Non-aqueous dispersion properties of pure barium titanate for tape casting

The dispersion properties of concentrated (25.0 and 50.0 vol.%) dispersions of high purity barium titanate powder dispersed in a methyl ethyl ketone (MEK) -ethanol solvent of moderate dielectric constant were studied in an effort to improve the uniformity of tape cast and sintered bodies. An amphoteric phosphate ester surfactant was found to be an effective dispersant. The dispersion properties of the phosphate ester were subsequently investigated by rheological, adsorption, conductivity, and electrophoretic mobility methods in order to evaluate a dispersion mechanism.Optimum dispersion occurred at an azeotrope solution of MEK and ethanol. The barium titanate particles dispersed in dry solvents exhibited a greater degree of dispersion than particles dispersed in hydrated solvents. The adsorption isotherm for the adsorption of the phosphate ester onto barium titanate particle surfaces using dry solvents exhibited a well-defined plateau corresponding to monolayer surface coverage. The plateau was less well defined for particles dispersed in hydrated solvents. Polymer coverage remained essentially constant with varying solvent composition. Optimum dispersion and maximum zeta potential occurred at a concentration of phosphate ester which corresponded to initial monolayer coverage. A maximum in the zeta potential also occurred at the azeotrope solution of MEK-ethanol and again coincided with optimum dispersion.Conductivity data indicate a dynamic adsorption-desorption dissociation mechanism for the ionic phosphate ester at the solid/liquid interface. The adsorption and conductivity data indicate the mechanism of dispersion stability is a combination of electrostatic and steric phenomena.     

Synthesis and thermal decomposition of barium peroxytitanate to barium titanate

Barium peroxytitanate, Ba₂[Ti₂(O₂)₄(OH)₄(H₂O)₄], was synthesized and its thermal decomposition in the temperature range from 298 to 1173 K was investigated. The intermediates at 423, 533, 773 and 873 K were identified by means of quantitative analysis, IR spectroscopy and X-ray diffraction analysis. On the basis of the data obtained, a scheme of its thermal decomposition was suggested.Isothermal treatment was carried out at 873 and 973 K for different periods. The optimum conditions of preparation of tetragonal barium titanate with high crystallinity were determined, i.e. annealing for 390 min at 873 K.

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Zusammenfassung Bariumperoxotitanat Ba₂[Ti₂(O₂)₄(OH)₄(H₂O)₄] wurde dargestellt und seine thermische Zersetzung im Temperaturbereich 298–1173 K untersucht. Die bei 423, 533, 773 und 873 vorliegenden Zwischenprodukte wurden durch quantitative Analyse, IR-Spektroskopie und Röntgenbeugung untersucht. Nach den Ergebnissen wurde ein Ablaufschema der thermischen Zersetzung vorgeschlagen. Isotherme Behandlung über unterschiedliche Zeiten bei 873 und 973 K ergaben als optimale Bedingungen für die Präparation von Bariumtitanat hoher Kristallinität 390 min bei 873 K.

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-Ba₂[Ti(O₂)₄(OH)₄(H₂O)₄] — 298–1173 . , , 423, 533, 773 873 . . 873 973 . 873 390 .

     

Redox processes in highly yttrium-doped barium titanate

The changes of microstructure occurring during oxidation of the reduced form of yttrium-doped barium titanate have been studied. Samples were sintered under reduction conditions at and oxidized by annealing at high temperatures (1150 and 1350 °C) in air. Depending on yttrium concentration, the oxidation of the reduced form of the yttrium-doped BaTiO₃ caused precipitation of the phase Ba₆Ti₁₇O₄₀ or the phases Ba₆Ti₁₇O₄₀ and Y₂Ti₂O₇. The precipitates had well-defined orientational relationships with the perovskite matrix. Oxidation of the reduced form of doped barium titanate results in formation of the phase responsible for increase in the resistance of outer grain layers, which lie between grain boundaries and grain.     

Room-temperature biosynthesis of ferroelectric barium titanate nanoparticles

The syntheses of inorganic materials by biological systems is characterized by processes that occur close to ambient temperatures, pressures, and neutral pH, as is exemplified by biosilicification and biomineralization processes in nature. Conversely, laboratory-based syntheses of oxide materials often require extremes of temperature and pressure. We have shown here the extracellular, room-temperature biosynthesis of 4-5 nm ternary oxide nanoparticles such as barium titanate (BT) using a fungus-mediated approach. The tetragonality as well as a lowered Curie transition temperature in sub-10 nm particles was established, and the ferroelectricity in these particles was shown using Kelvin probe microscopy.     

Synthesis of single-crystalline perovskite nanorods composed of barium titanate and strontium titanate

We report the solution-based synthesis of single-crystalline nanorods composed of barium titanate (BaTiO3) and strontium titanate (SrTiO3), which yields well-isolated nanorods with diameters ranging from 5 to 60 nm and lengths reaching up to >10 mum. Electron microscopy and diffraction measurements show that these nanorods are composed of single-crystalline cubic perovskite BaTiO3 and SrTiO3 with a principal axis of the unit cell preferentially aligned along the wire length. These BaTiO3 and SrTiO3 nanorods should provide promising materials for fundamental investigations on nanoscale ferroelectricity, piezoelectricity, and paraelectricity.     

Liquid-phase synthesis of barium acetatotitanyl and barium oxalatotitanyl as intermediates for preparing nanosized barium titanate

Liquid-phase methods (an oxalate process in aqueous solution and a semialkoxide sol-gel process in anhydrous acetic acid) were used to prepare barium acetatotitanyl (BAT) and barium oxalatotitanyl (BOT), which are potential fillers for electrorheological liquids, and to prepare barium titanate during heat treatment of the aforementioned intermediates at 1200°C. The materials were characterized using electron microscopy, FTIR spectroscopy, and thermal analysis. The particle size was 80 to 100 nm for BAT powders and 20 to 50 nm for BOT powders. X-ray spectra of the powders dried at 120°C contain reflections from a barium titanate phase. The dielectric spectra of the materials synthesized were studied for suspensions in PMS-20 silicone oil over the frequency range from 25 to 10⁶ Hz up to 4 kV/mm. The dielectric parameters of BOT suspensions decrease hyperbolically with rising alternate current frequency, whereas BAT suspensions give rise to a relaxation dielectric spectrum with relaxation times on the order of 10⁻³ s.     

End-grafted low-molecular-weight PNIPAM does not collapse above the LCST

The interfacial properties of end-grafted temperature-responsive poly(N-isopropylacryamide) (PNIPAM) were quantified by direct force measurements both above and below the lower critical solution temperature (LCST) of 32 degrees C. The forces were measured between identical, opposing PNIPAM films and between a PNIPAM film and a lipid membrane. At the grafting densities and molecular weights investigated, the polymer extension did not change significantly above the LCST, and the polymers did not adhere. Below the LCST, the force-distance profiles suggest a vertical phase separation, which results in a diluter outer layer and a dense surface proximal layer. At large separations, the force profiles agree qualitatively with simple polymer theory but deviate at small separations. Importantly, at these low grafting densities and molecular weights, the end-grafted PNIPAM does not collapse above the LCST. This finding has direct implications for triggering liposomal drug release with end-grafted PNIPAM, but it increases the temperature range where these short PNIPAM chains function as steric stabilizers.     

Site-selective spectroscopy of the solid-state defect chemistry in erbium-doped barium titanate

Erbium-doped barium titanate crystals were studied by laser-induced fluorescence spectroscopy. Thirteen spectroscopically distinct erbium ion sites were found. The relative concentrations of the different sites changed as a function of the crystal and its preparation and treatment. One major site was present in all crystals. The site distribution was changed either by growing codoped crystals with donor (La3+) and acceptor (Sc3+) ions or by changing the temperature and partial pressure of the oxygen in the annealing atmosphere. Equilibrium calculations were done to simulate the defect distributions that result from the charge compensation of the erbium ions. Comparison with the observed dependence of the site spectral intensities indicated that the erbium enters the lattice on barium sites. We assigned the dominant site to an erbium ion on a barium site that is locally compensated by a barium vacancy, whereas the other lower-intensity sites corresponded to erbium ions that are locally compensated by an electron and a more complex center of an erbium, a barium vacancy, and a hole. The spectra of one sample showed that its defects were different and were characteristic of a sample that had not equilibrated. The new sites in this sample were assigned to erbium entering the lattice on a titanium site, which was then locally compensated by an oxygen vacancy or a hole. Heating equilibrated the sample and changed the erbium to a barium site.     

Probing the multifunctional behaviour of barium zirconate/barium titanate/epoxy resin hybrid nanodielectrics

Journal of Thermal Analysis and Calorimetry - In this study, thermodynamic analysis of a supercritical closed Brayton cycle integrated with parabolic trough solar collectors operating with various...     

Mechanistic investigations on the densification behaviour of barium titanate ceramics

The processes occurring during the densification of La_0.002Ba_0.998TiO₃ powders with different SiO₂-containing additives (TiO₂+SiO₂), (CaO+TiO₂+SiO₂), (2BaO+TiO₂+2SiO₂) have been investigated using a step-like annealing of the compacts. The reactions taking place during isothermal dwelling and their effects on the shrinkage rates in the following heating period have been characterized. The samples dwelt for 30 minutes exhibited a higher shrinkage rate than the compacts dwelt for 120 minutes. X-ray diffraction measurements revealed that the differences between both dwelling times are caused by the differences in the structural activity of the powders, i.e. by the reaction-mediated formation and degradation of defects in the surface regions of the BaTiO₃ grains. The process of formation of the Ba₂TiSi₂O₈ phase which acts as a defect source is kinetically preferred to the formation of the Ba₄Ti₁₃O₃₀ phase which acts as a defect drain. Thus, during short dwelling times defect-rich surfaces of the BaTiO₃ grains and/or glass-like intermediates are created. These structures favour the sliding of whole grains and consequently result in high shrinkage rates. The gradual degradation of these thermodynamically unstable structures by the formation of the Ba₄Ti₁₃O₃₀ phase during prolonged dwelling times deteriorates the sliding properties of the grains and reduces the shrinkage rate.     

Photoluminescence of barium titanate and barium zirconate in multilayer disordered thin films at room temperature

The emission of wide band photoluminescence showed a synergic effect on barium zirconate and barium titanate thin films in alternate multilayer system at room temperature by 488 nm exiting wavelength. The thin films obtained by spin-coating were annealed at 350, 450, and 550 degrees C for 2 h. The X-ray patterns revealed the complete separation among the BaTiO3 and BaZrO3 phases in the adjacent films. Visible and intense photoluminescence was governed by BaZrO3 thin films in the multilayer system. Quantum mechanics calculations were used in order to simulate ordered and disordered thin films structures. The disordered models, which were built by using the displacement of formers and modifier networks, showed a different symmetry in each system, which is in accordance with experimental photoluminescence emission, thus allowing to establish a correlation among the structural and optical properties of these multilayered systems.     

Diffusion in polyacrylic acid aqueous solutions

The four diffusion coefficients for the ternary system polyacrylic acid (mol. weight 5000)-polyacrylic acid (mol. weight 115000)-water have been measured at 25°C and at one average polyelectrolytes concentration. The experimental values of main and cross terms have been briefly discussed. The large cross term D ₁₂ in the system with water as solvent shows that, contrary to intuition, different molecular weight species do interact with each other.     

ESR spectra of irradiated polyacrylic acid

In view of the interest in acrylic acid co-polymerized with other polymers by radiation to promote enhanced crosslinking, a knowledge of the intermediate reaction products is highly desirable. ESR techniques have been used to study the nature and stability of the radicals formed. Acrylic acid was polymerized by exposure to gamma radiation; the nature of the radicals, their decay at various temperatures, and the effect of inhibitors were investigated.The ESR spectrum at room temperature is similar to that described by earlier workers; its dependence on temperature and impurities, as well as its decay, were investigated. From this work, there is reason to believe that the described triplet also contains a central singlet of ΔH_ms19 G; the addition of impurities to the acrylic acid causes the triplet to decay more rapidly, thus leaving the predominant singlet mentioned above. It was also found that the lines in the outer “wings” of the irradiated specimen disappear on heating; at the same time a new line, possibly a singlet of ΔH_ms131 G, either became more intense or more obvious. Some tentative explanations of this behaviour are advanced.     

Gamma-resonance investigation of iron-containing polyacrylic acid

Journal of Structural Chemistry -     

Temperature-dependence of electromechanical coupling and strain in barium titanate hafnate transducer

The electromechanical coupling factor and ferroelectric hysteresis loops were investigated at different temperatures for BaTi_0.85Hf_0.15O₃ transducer. Maximum polarization and strain were obtained near the transition of the crystal structure. This correlated with increases in the ease and extent of ferroelectric domain boundary motion. The change in the crystal structure varied the unit cell volume, leading to higher strain.

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Zusammenfassung Der elektromechanische Kopplungsfaktor und die ferroelektrische Hysteresisschleife wurde für BaTi_0.85Hf_0.15O₃-Transducer bei verschiedenen Temperaturen untersucht. Polarisation und Deformation nehmen in der Nähe des Umwandlungspunktes der Kristallstruktur maximale Werte an. Dies korreliert mit Leichtigkeit und Außmaß der Grenzbewegung im ferromagnetischen Bereich. Die mit der Umwandlung der Kristallstruktur zusammenhängende Veränderung des Elementarzellenvolumens führt zu größerer Verformung.

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BaTi_0.85Hf_0.15O₃ . . . , .

     

Toward a more environmentally benign synthesis of doped barium titanate

Abstract

Barium titanate is one of the most thoroughly studied members of the perovskite family due to its prominent place in the electroceramic industry. To be used as a capacitor at room temperature, a high-dielectric constant is needed which is achieved through doping. The focus of this research was to develop a more environmentally benign alternative to the doping of barium titanate. The barium source was barium titanyl catecholate, Ba[Ti(cat)₃] (aq) and the doping sources were strontium oxalate (SrC₂O₄) and strontium carbonate (SrCO₃). The doping strategies included a solid-state synthetic pathway as well as microwave- and centrifuge-assisted methods which both employed water as the only solvent. The last two benign by design methods were tested with respect to their thermodynamic control over barium-to-strontium stoichiometric ratios. These methods of doping proved to be more environmentally friendly and economical while combining green chemistry and materials science.     

High-temperature degradation of polyacrylic acid in aqueous solution

Poly(acrylic acid) (PAA) was decarboxylated in aqueous solution as a function of pH and ionic strength in the temperature range 100–350°C. Degradation kinetics were first order with respect to acid functionality. The rate of decarboxylation at high pH (E_α = 51.1 kcal/mol) was much slower than that at low pH (E_α = 20.3 kcal/mol). At intermediate pH, the reactivity was found to depend on the degree of dissociation of PAA as a functions of ionic strength, pH, and temperature. No monomer was observed in the reaction product. © 1996 John Wiley & Sons, Inc.     

Synthesis of barium titanate/polymer composites from metal alkoxide

Barium titanate (BaTiO₃)/polymer composite was successfully synthesized by methacryltriisopropoxytitanium (MTPT) and barium alkoxide. MTPT undergoes radical polymerization using azobisisobutyronitrile at temperatures from 90 to 150°C. ¹H NMR spectra showed that MTPT reacted with barium alkoxides yielding a complex alkoxide. BaTiO₃ particles/polymer was formed after the polymerization and hydrolysis of the complex alkoxide. The transmission electron microscopic observation revealed that crystalline BaTiO₃ particles of around 3 nm in size were dispersed in the polymer matrix.     

Removal of uranyl ions from aqueous solutions using barium titanate

Remediation of water sources contaminated with radioactive waste products is a major environmental issue that demands new and more efficient technologies. For this purpose, we report a highly efficient ion-exchange material for the removal of radioactive nuclides from aqueous solutions. The kinetic characteristics of adsorption of uranyl ions on the surface of barium titanate were investigated using a spectrophotometric method under a wide range of conditions. By controlling the pH it was possible to exert fine control over the speciation of uranium, and by optimizing the temperature and grain size of the exchanger, almost total removal was achieved in a matter of just hours. The highest efficiency (>90 % removal) was realized at high temperature (80 °C). Moreover, the effect of competitive ion adsorption from a range of different cations and anions was quantified. Adsorption was found to follow first-order kinetics and both Freundlich and Langmuir isotherms could be applied to this system. The results of a mathematical treatment of the kinetic data combined with the observation that adsorption was independent of stirring speed and dependent on the ion-exchanger grain size, indicate that the dominant mechanism influencing adsorption is particle spreading. The adsorption behavior was not influenced by exposure to high-intensity gamma radiation, indicating potential for use of this ion-exchanger in systems containing radioactive material. These results will be of use in the development of uranium extraction systems for contaminated water sources.     

Approaches for enhancing the photocatalytic activities of barium titanate: A review

Barium titanate(Ba TiO₃), a dielectric/ferroelectric semiconductor with perovskite structures is the most widely used photocatalyst in the field of environmental applications due to its low-cost, chemical stability, and non-toxicity. Different types and forms of Ba TiO₃have shown their great potential toward the significant photocatalytic reactions owing to the several beneficial properties, including appropriate band positions, high oxygen vacancies, multiple crystal struc...