Effect of sintering atmosphere on the microstructure and dielectric properties of barium strontium titanate glass–ceramics

The sintering of barium strontium titanate glass–ceramics in nitrogen modified their dielectric properties significantly compared to the sintering in air. The experimental results demonstrate that the glass–ceramics sintered at low temperatures contain a major phase Ba₂TiSi₂O₈ (BTS), known as fresnoite. The fresnoite phase disappeared and the barium strontium titanate perovskite phase became the major phase when the sintering temperature was increased. In addition, the microstructure observation showed that both the proportion of crystal phase and the crystal size increase obviously with the increase of sintering temperature. Most importantly, impedance spectroscopy has been employed to study the electrical responses arising from the glass and the crystal phases in the glass–ceramics sintered at low temperatures and high temperatures. The magnitudes of impedance and modulus changed significantly for the glass–ceramics sintered at the two temperature ranges. The activation energy calculated from the complex impedance, complex modulus and dc conductivity suggests that the dielectric relaxation for the glass phase and the glass–crystal interface may be attributed to the motion of the dipole associated with oxygen vacancy. And for the barium strontium titanate perovskite glass–ceramics, the motion of the electrons from the second ionization of oxygen vacancies leads to dc electrical conduction. The mechanism for the giant dielectric properties of the glass–ceramics sintered at high temperatures in nitrogen is discussed.     

Effect of La2O3 additive on the dielectric properties of barium strontium titanate glass–ceramics

The barium strontium titanate (Ba_xSr_1–xTiO₃) glass–ceramics doped with different content of La were prepared via controlled crystallization. Phase compositions, microstructure and dielectric behaviors were investigated systematically. The results revealed that La₂O₃ additives had little influence on the dielectric constant but significantly changed the microstructure of the glass–ceramics, which led to improved breakdown strength (BDS). The optimized energy-storage density of 3.18 J/cm³ was achieved in the glass–ceramics with 1.0 wt% La₂O₃ content which is 2.56 times higher than pure BST glass–ceramics, suggesting glass–ceramics of this composition could be an attractive candidate for energy-storage applications.     

Low temperature synthesis and characterization of strontium stannate–titanate ceramics

A novel modified chimie douce synthetic approach based on the gel to crystallite conversion (G–C) method has been developed to prepare strontium titanate SrTiO₃, strontium stannate SrSnO₃, and mixed strontium stannate–titanate SrSn_1−xTi_xO₃ (x = 0.05–0.5). The obtained materials were characterized by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). The formation of fully crystalline SrTiO₃ was observed in the temperature range of 800–1000 °C. The formation of monophasic SrSnO₃ occurs in the temperature range of 700–900 °C. At lower and higher temperatures the formation an impurity phases such as SrCO₃ and SnO₂ takes place. The same synthetic approach has been applied for the preparation of mixed strontium stannates–titanates SrSn_1−xTi_xO₃. The SEM images of SrTiO₃ samples indicated that the powder particles are 1–5 μm in size having approximately plate-like shape. Quite different surface morphology was determined for SrSnO₃ samples revealing the size of crystals from 500 nm to 40 μm. For the composition with x = 0.15, it was observed that the grain growth is uniform and the size of the grains is of the order of ∼2–5 μm.     

Structure and ferroelectric properties of barium titanate films synthesized by sol–gel method

The barium strontium titanate (Ba_0.7Sr_0.3TiO₃, BST) thin films were synthesized by a sol–gel technique on a silicon nanoporous pillar array (Si-NPA) substrate. SEM observation reveals that the as-prepared BST thin film has uniformly covered the inherited pillar-like surface of the Si-NPA substrate. X-ray diffraction analysis indicates that the perovskite phase was able to be generated in the BST film when the annealing temperature was higher than 600 °C. The remnant polarization (Pr) and coercive field (Ec) values were also found to increase with the annealing temperature, with the maxima of 4.57 μC cm⁻² for Pr and 7.61 kV mm⁻¹ for Ec at 800 °C, respectively. The measurement of leakage current density against voltage applied suggested that the BST films are excellent insulators along with fair resistance to breakdown, and the mechanism of leakage current was discussed.     

Magnetic properties of Ni–Co doped barium strontium hexaferrite

A series of Ni–Co substituted barium strontium hexaferrite materials, Ba_0.5Sr_0.5Ni _x Co _x Fe_12–2x O₁₉ (x = 0.0, 0.2, 0.4, 0.6, 0.8 mol%) was synthesized by the sol–gel method. X-ray diffraction analysis has shown that the Ni–Co substitutions maintain in a single hexagonal magnetoplumbite phase. The room temperature magnetic properties and the cation site preferences of Ni–Co substituted ferrite were investigated by VSM. Substitutions led to decrease in coercivity while saturation magnetization remains the almost same. It indicates that the saturation magnetization (52.81–59.8 Am²/kg) and coercivity (69.83–804.97 Oe) of barium strontium hexaferrite samples can be varied over a very wide range by an appropriate amount of Ni–Co doping contents.     

Selective laser sintering of barium titanate–polymer composite films

A selective laser sintering process has been used to consolidate electro-ceramic thin films on silicon substrates. Methods of forming pre-positioned layers of barium titanate were investigated by spin-coating the feedstock powder mixed with a commercial polymer photo-resist. The ceramic–polymer composite was deposited directly onto a nickel film which was evaporated onto a silicon substrate, pre-oxidised to form an electrically insulating layer. A range of laser processing parameters was identified in which consolidated barium titanate layers could be formed. The laser power was found to be more influential in forming sintered microstructures than laser exposure time. The microstructure of barium titanate films is sensitive to the SLS laser-processing conditions, with the optimum laser powers for the processing of the BaTiO₃–polymer found to be in the range 17–20 W. This article highlights the possibility of using ‘direct write’ techniques to produce piezoelectric materials upon silicon substrates.     

Preparation and magnetic properties of Ni–Zr doped barium strontium hexaferrite

M-type Hexaferrites B_0.5Sr_0.5Fe_12−2x Ni _x Zr _x O₁₉ were synthesized and investigated. The XRD patterns show single phase of the magnetoplumbite barium strontium ferrite and no other phases were present. The samples exhibit well defined crystallization; all of them are hexagonal platelet grains. As the substitution level increased from x = 0.2 to 0.8 mol%, the grains are agglomerated and the average diameter increased. This suggests that Ni–Zr substitution increases the grain size, as observed in the FE-SEM micrographs. The results of magnetic measurement revealed that M_s of barium strontium hexaferrite increased when the value of x increased from 0 to 0.4 mol% and then decreased with the increasing Ni–Zr content. The H_c decreases remarkably with increasing Ni and Zr ions content. Hard magnetic material is converted into soft magnetic material when the substitution level is increased from 0.2 to 0.8 mol%. In particular, Ba_0.5Sr_0.5Fe_12−2x Ni _x Zr _x O₁₉ with x = 0.2, 0.4, 0.6, 0.8 mol% has suitable magnetic characteristics with particle size small enough for high-density magnetic recording applications.     

UV–LED driven photodegradation of organic dye and antibiotic using strontium titanate nanostructures

Journal of Materials Science: Materials in Electronics - In the present study, SrTiO3 (strontium titanate) photocatalyst was prepared through the hydrothermal process for photodegradation of...     

Nanothickness films,nanostructured films,and nanocrystals of barium titanate obtained directly by a newly developed sol–gel synthesis pathway

This work aims to develop a chemically modified sol–gel synthesis pathway for obtaining various barium titanate nanostructures. The method is able to prepare different BaTiO₃ nanostructures such as highly stable nanoparticle embedded colloids, highly transparent amorphous nanolayers, nanocrystalline BaTiO₃ powders and ultrathin BaTiO₃ nanostructured films directly from a precursor solution. All the products have been prepared at a lower temperature and in a more cost-effective way in contrast to other established sol–gel methods. The results show that the optical transparency of the thin films has been significantly improved in contrast to the similar researches. The deposited thin film is highly transparent with an average transmission of 87 % in the wavelength range from 400 to 1,200 nm, which this transparency is higher than the reported values in the similar researches in those, the average transmissions in the range of 70–75 % have been reported. From the study of the relationships between structure and properties of the products, it is found that the optical transparency enhancement in the thin films is due to the size of the particles within the precursor solution, which is in the range of a few nanometers. The above-mentioned advantages have been reached thanks to the applied modifications, which result in the drastic downsizing the particles within the precursor solution.     

On the sol–gel synthesis and characterization of strontium ferrite ceramic material

A simple oxalate based sol–gel process has been described to produce a highly stable anion deficient strontium ferrite for separation of oxygen from air. The method involves metal nitrates and oxalic acid precursors with ethanol and water as solvents, gel formation, digestion for 4 h, drying at 150 °C for 24 h, and finally decomposition at 800 °C in air. The resulting material (i) exhibits a single perovskite-type cubic (SrFeO_3?ξ; ξ ～ 0.13) phase with a_o = 3.862 ± 0.002 Å, (ii) contains both the Fe⁴⁺ and Fe³⁺ species in 2.8:1 ratio, (iii) undergoes Fe⁴⁺ → Fe³⁺ reduction upon heating at 650 °C in rare gas ambient and transition to an orthorhombic phase with a ～ a_o√2, b ～ 4a_o, c ～ a_o√2, which reverts back to cubic phase with oxygen uptake at elevated temperatures, and (iv) acts as filter for air with excellent oxygen permeation, typical flux density value being 2.45 ml/cm² min at 1000 °C.     

Microstructural characterization of donor-doped lead zirconate titanate films prepared by sol–gel processing

Lanthanum and niobium-doped lead zirconate titanate, Pb(Zr,Ti)O₃, (PZT) thin films were prepared on Pt/Ti/SiO₂/Si substrates by sol–gel processing. Films have a Zr/Ti ratio of 52:48 and tetragonal perovskite phase structure. The influence of donor dopants on the morphology, texture and defects of PZT films was studied using X-ray diffraction, X-ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy, breakdown field strength and fatigue. Donor doping of PZT films results in increased breakdown field strength and improved fatigue properties. These originate from (i) the reduction of texture in the [111] and increase in the texture in [100]; (ii) lower porosity, smaller grain size and smoother surfaces; (iii) granular grain structure; and (iv) reduction in the oxygen vacancy concentration in the films.     

Synthesis and characterization of pyrochlore-type yttrium titanate nanoparticles by modified sol–gel method

Pyrochlore-type yttrium titanate (Y₂Ti₂O₇) nanoparticles were successfully synthesized by a simple soft-chemistry technique viz. citric acid sol–gel method (CAM). The preparation process was monitored by X-ray diffraction, thermogravimetric–differential thermal analysis and Fourier transform–infrared experiments and the microstructures and average size of as-prepared products were characterized by transmission electron microscopy and high resolution transmission electron microscopy images. It was found that compared with traditional solid state reaction (SSR), Y₂Ti₂O₇ nanopowders were synthesized at a relatively low temperature (750°C) for shortened reaction time. Detailed analysis showed that the as-prepared Y₂Ti₂O₇ with good dispersibility and narrow size distribution were quasi-spherical; the average size was about 20–30 nm, also, the obtained products had higher BET surface area (50 m²/g). These properties are very helpful for a photocatalyst to achieve excellent activity and may result in better behaviour in hydrogen storage.     

Water-based sol–gel nanocrystalline barium titanate: controlling the crystal structure and phase transformation by Ba:Ti atomic ratio

Highly stable, water-based barium titanate (BaTiO₃) sols were developed by a low cost and straightforward sol–gel process. Nanocrystalline barium titanate thin films and powders with various Ba:Ti atomic ratios were produced from the aqueous sols. The prepared sols had a narrow particle size distribution in the range 21–23 nm and they were stable over 5 months. X-ray diffraction pattern revealed that powders contained mixture of hexagonal- or perovskite-BaTiO₃ as well as a trace of Ba₂Ti₁₃O₂₂ and Ba₄Ti₂O₂₇ phases, depending on annealing temperature and Ba:Ti atomic ratio. Highly pure barium titanate with cubic perovskite structure achieved with Ba:Ti = 50:50 atomic ratio at the high temperature of 800 °C, whereas pure barium titanate with hexagonal structure obtained for the same atomic ratio at the low temperature of 500 °C. Transmission electron microscope revealed that the crystallite size of both hexagonal- and perovskite-BaTiO₃ phases reduced with increasing the Ba:Ti atomic ratio, being in the range 2–3 nm. Scanning electron microscope analysis revealed that the average grain size of barium titanate thin films decreased with an increase in the Ba:Ti atomic ratio, being in the range 28–35 nm. Moreover, based on atomic force microscope images, BaTiO₃ thin films had a columnar-like morphology with high roughness. One of the highest specific surface area reported in the literature was obtained for annealed powders at 550 °C in the range 257–353 m²g⁻¹.     

Phase formation and high dielectric constant of calcium copper titanate using sol–gel route

Nano-sized calcium copper titanate (CCTO) powder was synthesized from a quick and innovative sol–gel process. Calcium nitrate, copper nitrate and titanium isopropoxide were used as the raw materials to synthesize the precursor product. The dried precursor powder was then milled and calcined at 450, 550, 650, 800, 850 and 950 °C for 3 h. The XRD results of the powder calcined at 800 °C indicates the formation of CCTO single phase. AFM studies shows that the average particle size of CCTO powder ranges around 80 nm. From the FTIR spectra the modes observed at 606, 525 and 463 cm⁻¹ was assigned to vibration modes of Ca–O, Cu–O and Ti–O–Ti, respectively. The samples sintered at 1,040 °C shows high density (96%) as compared to the theoretical value. The grain sizes of sintered pellets were determined by FE-SEM and the dielectric properties were studied by LCR meter.     

Effect of process conditions on phase mixtures of sol–gel-synthesized nanoscale orthorhombic, tetragonal, and monoclinic zirconia

Zirconia particles synthesized under ambient conditions are frequently amorphous, requiring heat to produce a crystalline phase. Synthesized nanoparticles are generally found in the tetragonal phase. In this article, a room temperature sol–gel synthesis of crystalline sub-10-nm zirconia particles is described. By adjusting the acid concentration of the reaction, it is found that the particles’ crystalline phase can be modified. Under acidic conditions with moisture present, the tetragonal phase is produced, whereas under acidic conditions with low water content, 2–5-nm particles suggestive of the metastable orthorhombic phase are produced. Subsequent heat treatment of all powders produced with this technique resulted in their transformation first to the tetragonal phase, and ultimately to the monoclinic phase. The extent of the transformation to the monoclinic phase depends upon the atmosphere, however, suggesting that oxygen vacancies play a significant role in the stabilization and determination of the resulting phase.     

Role of particle size of alumina on the formation of aluminium titanate as well as on sintering and microstructure development in sol–gel alumina–aluminium titanate composites

With a view to develop low temperature fine grained alumina–aluminium titanate composite, influence of alumina particle size on the temperature of formation of the aluminium titanate, sintering behaviour and microstructure development of alumina–aluminium titanate composite prepared through a sol–gel core shell approach is reported. The alumina matrix composite containing 20 wt% aluminium titanate has been prepared from alumina powders having different average particle size in the range 300–600 nm. The alumina particle size appears to have no significant influence on the formation temperature of in situ formed aluminium titanate. However, the microstructural analysis of the dense ceramic showed that the average grain size of the alumina–aluminium titanate composite increases with increase in the alumina particle size. XRD analysis indicated the absence of rutile titania in the sintered composite ensuring complete formation of aluminium titanate. Smaller starting alumina particle size led to finer grain size composites. The present study therefore shows that although the starting particle size of alumina has no significant role on the lowering of formation temperature of aluminium titanate, it does influence the microstructure of the composite.