Colossal Permittivity Characteristics of (Nb, Si) Co-Doped TiO2 Ceramics.

(Nb5+, Si4+) co-doped TiO2 (NSTO) ceramics with the compositions (Nb0.5Si0.5)xTi1−xO2, x = 0, 0.025, 0.050 and 0.1 were prepared with a solid-state reaction technique. X-ray diffraction (XRD) patterns and Raman spectra confirmed that the tetragonal rutile is the main phase in all the ceramics. Additionally, XRD revealed the presence of a secondary phase of SiO2 in the co-doped ceramics. Impedance spectroscopy analysis showed two contributions, which correspond to the responses of grain and grain-boundary. All the (Nb, Si) co-doped TiO2 showed improved dielectric performance in the high frequency range (>103 Hz). The sample (Nb0.5Si0.5)0.025Ti0.975O2 showed the best dielectric performance in terms of higher relative permittivity (5.5 × 104) and lower dielectric loss (0.18), at 10 kHz and 300 K, compared to pure TiO2 (1.1 × 103, 0.34). The colossal permittivity of NSTO ceramics is attributed to an internal barrier layer capacitance (IBLC) effect, formed by insulating grain-boundaries and semiconductor grains in the ceramics.

Dielectric Properties of Bi2/3Cu3Ti4O12 Ceramics Prepared by Mechanical Ball Milling and Low Temperature Conventional Sintering.

In the current study, Bi2/3Cu3Ti4O12 (BCTO) ceramics were prepared by mechanical ball mill of the elemental oxides followed by conventional sintering of the powder without any pre-sintering heat treatments. The sintering temperature was in the range 950-990 °C, which is 100-150 °C lower than the previous conventional sintering studies on BCTO ceramics. All the ceramic samples showed body-centered cubic phase and grain size ≈ 2-6 µm. Sintering temperature in the range 950-975 °C resulted in comparatively lower dielectric loss and lower thermal coefficient of permittivity in the temperature range from -50 to 120 °C. All the BCTO ceramics showed reasonably high relative permittivity. The behavior of BCTO ceramics was correlated with the change in oxygen content in the samples with sintering temperature. This interpretation was supported by the measurements of the energy dispersive x-ray spectroscopy (EDS) elemental analysis and activation energy for conduction and for relaxation in the ceramics.

Dielectric Properties of Colossal-Dielectric-Constant Na1/2La1/2Cu3Ti4O12 Ceramics Prepared by Spark Plasma Sintering.

In the current study, we report on the dielectric behavior of colossal-dielectric-constant Na1/2La1/2Cu3Ti4O12 (NLCTO) ceramics prepared by mechanochemical synthesis and spark plasma sintering (SPS) at 850 °C, 900 °C, and 925 °C for 10 min. X-ray powder diffraction analysis showed that all the ceramics have a cubic phase. Scanning electron microscope observations revealed an increase in the average grain size from 175 to 300 nm with an increase in the sintering temperature. SPS NLCTO ceramics showed a room-temperature colossal dielectric constant (>103) and a comparatively high dielectric loss (>0.1) over most of the studied frequency range (1 Hz-40 MHz). Two relaxation peaks were observed in the spectra of the electrical modulus and attributed to the response of grain and grain boundary. According to the Nyquist plots of complex impedance, the SPS NLCTO ceramics have semiconductor grains surrounded by electrically resistive grain boundaries. The colossal dielectric constant of SPS NLCTO ceramics was attributed to the internal barrier layer capacitance (IBLC) effect. The high dielectric loss is thought to be due to the low resistivity of the grain boundary of SPS NLCTO.

An Effective Photocatalytic Degradation of Industrial Pollutants through Converting Titanium Oxide to Magnetic Nanotubes and Hollow Nanorods by Kirkendall Effect.

Controlling of morphology from nanoparticles to magnetic nanotubes and hollow nanorods are interesting for developing the photo-active materials and their applications in the field of photocatalysis and decontamination of aquatic effluents. In the current study, titanium dioxide nanoparticles and nanocomposites were prepared by different techniques to produce various morphologies. The nanoparticles of pure titanium dioxide were prepared by sol-gel technique. Magnetic nanotubes and hollow nanorods were prepared by combining titanium with di- and tri-valent iron through two stages: urea hydrolysis and solvent thermal technique. According to the Kirkendall effect, magnetic nanotubes were fabricated by unequal diffusion of Fe2+, Fe3+ and Ti4+ inside the nanocomposite to produce maghemite-titanian phase. In the same trend, hollow nanorods were synthesized by limited diffusion of both trivalent iron and tetravalent titanium producing amorphous structure of titanium iron oxides. The magnetic and optical properties showed that these nanotubes and hollow nanorods are magnetically active and optically more effective compared with titanium dioxide nanoparticles. Therefore, the Naphthol green B dye completely disappeared after 45 min of UV light irradiation in presence of the hollow nanorods. The kinetic study confirmed the high performance of the hollow nanorods for the photocatalytic degradation of Naphthol green B compared with titanium dioxide nanoparticles.

Sintering Temperature, Frequency, and Temperature Dependent Dielectric Properties of Na0.5Sm0.5Cu3Ti4O12 Ceramics.

NSCTO (Na0.5Sm0.5Cu3Ti4O12) ceramics have been prepared by reactive sintering solid-state reaction where the powder was prepared from the elemental oxides by mechanochemical milling followed by conventional sintering in the temperature range 1000-1100 °C. The influence of sintering temperature on the structural and dielectric properties was thoroughly studied. X-ray diffraction analysis (XRD) revealed the formation of the cubic NSCTO phase. By using the Williamson-Hall approach, the crystallite size and lattice strain were calculated. Scanning electron microscope (SEM) observations revealed that the grain size of NSCTO ceramics is slightly dependent on the sintering temperature where the average grain size increased from 1.91 ± 0.36 µm to 2.58 ± 0.89 µm with increasing sintering temperature from 1000 °C to 1100 °C. The ceramic sample sintered at 1025 °C showed the best compromise between colossal relative permittivity (ε' = 1.34 × 103) and low dielectric loss (tanδ = 0.043) values at 1.1 kHz and 300 K. The calculated activation energy for relaxation and conduction of NSCTO highlighted the important role of single and double ionized oxygen vacancies in these processes.

Dielectric Response and Structural Analysis of (A3+, Nb5+) Cosubstituted CaCu3Ti4O12 Ceramics (A: Al and Bi).

CaCu3Ti4-x((A0.05Nb0.05))xO12 ceramics (A: Al and Bi; x = 0, 0.3) were synthesized by high-energy mechanical ball milling and reactive sintering at 1050 °C in air. Rietveld refinement of XRD data revealed the pure and (Al3+, Nb5+) cosubstituted ceramics contained a minor CuO secondary phase with a mole fraction of about 3.2% and 6.9%, respectively, along with a CaCu3Ti4O12 (CCTO)-like cubic structure. In addition, (Bi3+, Nb5+) cosubstituted ceramics had a pyrochlore (Ca2(Ti, Nb)2O7) secondary phase of about 18%. While the (Al3+, Nb5+) cosubstituted CCTO showed the highest relative permittivity (ε' = 3.9 × 104), pure CCTO showed the lowest dielectric loss (tanδ = 0.023) at 1 kHz and 300 K. Impedance-spectroscopy (IS) measurements showed an electrically heterogeneous structure for the studied ceramics, where a semiconducting grain was surrounded by highly resistive grain boundary. The giant relative permittivity of the ceramics was attributed to the Maxwell-Wagner polarization effect at the blocking grain boundaries and domain boundaries. The higher tanδ of the cosubstituted samples was correlated with their lower grain boundary's resistivity, as confirmed by IS analysis. Modulus-spectrum analysis revealed two relaxation processes for the pure and (Bi3+, Nb5+) cosubstituted CCTO samples. Dissimilar behavior was observed for the (Al3+, Nb5+) cosubstituted CCTO, where three relaxation mechanisms were observed and attributed to the grain, domain-boundary, and grain-boundary responses.