Mechanochemical-molten salt synthesis of Na2Ti6O13 nanobelts

A novel route for the preparation of Na₂Ti₆O₁₃ nanobelts by mechanochemical treatment of the TiCl₄-Na₂SO₄·10H₂O-Na₂CO₃ mixture for 5 min followed by molten salt synthesis is described. The mixture of the amorphous TiO₂ and NaCl-Na₂SO₄·xH₂O-Na₂CO₃ salt matrix was generated during milling. The molten salt synthesis of the Na₂Ti₆O₁₃ nanobelts with lengths up to 0.5-2 μm and with a width in the range of 20-250 nm was carried out in the temperature range of 700-800 °C for 1 h. The partial formation of titanate nanotubes was observed after annealing at 600 °C and washing procedure. X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential thermal analysis (DTA) were used to characterize the formation and structure of Na₂Ti₆O₁₃ nanobelts.     

Hydrothermal synthesis and properties of solid solutions and composite nanoparticles in the TiO2-SnO2 system

Solid solutions and composite nanoparticles in the TiO₂-SnO₂ system were directly formed via the hydrothermal treatment of precursor solutions of TiCl₄ and SnCl₄ under weakly basic conditions in the presence of urea. The rutile-type (Ti, Sn)O₂ solid solutions were formed in the composition range of Ti 0-70 mol%. The composite nanoparticles consisting of anatase- and rutile-type phases were formed at the composition of Ti 80 and Ti 90 mol%. The change in the lattice parameters a₀ and c₀ of the rutile-type solid solutions followed the Vegard Law. The crystallite size of the rutile-type solid solutions was in the range of 5-10 nm. The diffuse reflectance spectra varied with changing Ti content in the precipitates. The photocatalytic activity of composite nanoparticles synthesized at 240 °C was higher than that synthesized at 180 °C. The composite nanoparticles consisting of anatase- and rutile-type phases with compositions Ti_0.90Sn_0.10O₂ and Ti_0.80Sn_0.20O₂ showed improved photocatalytic activity.     

Electrical properties of Pb0.97La0.02(Zr0.95Ti0.05)O3 antiferroelectric thin films on TiO2 buffer layer

Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ antiferroelectric thin films with thickness of 500 nm were successfully deposited on TiO₂ buffered Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) and Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates via sol-gel process. Microstructure of Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ thin films was studied by X-ray diffraction analyses. The antiferroelectric nature of the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ thin films was confirmed by the double hysteresis behaviors of polarization and double buffer fly response of dielectric constant versus applied voltage at room temperature. The capacitance-voltage behaviors of the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ films with and without TiO₂ buffer layer were studied, as a function of temperature. The temperature dependence of dielectric constant displayed a similar behavior and the Curie temperature (T_c) was 193 °C for films on both substrates. The current caused by the polarization and depolarization of polar in the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ films was detected by current density-electric field measurement.     

Structural and electrical properties of Na2Pb2Eu2W2Ti4X4O30 (X = Nb, Ta) ferroelectric ceramics

A new group of tungsten bronze family Na₂Pb₂Eu₂W₂Ti₄X₄O₃₀ (X = Nb, Ta) having all the valence elements (I-VI) were prepared by a high-temperature solid-state reaction technique. The formations of the compounds were confirmed by X-ray diffraction technique with an orthorhombic structure. Surface morphology of the compounds was studied by scanning electron microscope (SEM). Studies of dielectric properties (?_r and tan δ) of the above compounds at different frequencies in a wide temperature range (300-700 K) with an impedance analyzer exhibit a ferroelectric phase transition at 580 and 394 K for Na₂Pb₂Eu₂W₂Ti₄Nb₄O₃₀ and Na₂Pb₂Eu₂W₂Ti₄Ta₄O₃₀, respectively. Ferroelectric properties of these compounds were confirmed with polarization (hysteresis) study.     

Effect of photocatalytic activities of nano-sized copper molybdate (CuMoO4)-doped bismuth titanate (Bi2Ti4O11) (CMBT) alloy

Different compositions of [CuMoO₄]_x-doped Bi₂Ti₄O₁₁ nanophotocatalyst (x = 0.05, 0.1, 0.5) have been prepared by chemical precursor decomposition (CPD) method using triethanolamine (TEA) and HNO₃. Cu(II) is one of reactive species on the catalyst surface and Mo(VI) ion helps to generate charge compensation of lattice having poor catalytic properties. The photocatalytic properties based on the prepared samples for photodecolorization of thymol blue (TB) solutions are examined by Hg-lamp. The crystal structures of the prepared nano-powders are characterized by XRD, EDAX, UV-vis spectra, specific surface area (BET), and HRTEM analyses. The average particle size of copper molybdate-doped bismuth titanate ranges 32 ± 5 nm measured from TEM. Results show doping of copper molybdate of 5 mol% with bismuth titanate can significantly increase the photoactivity of bismuth titanate compared all the compositions studied except degussa P25 titania. The observed increased photocatalytic activity of copper molybdate-doped bismuth titanate ((CuMoO4)_x(Bi₂Ti₄O₁₁)_1−x; CM_xBT_1−x) is attributed to the strong absorption of OH groups at the surface of the catalyst.     

Crystal structures of CdTi2O4(OH)2 and LaTiSbO6

The crystal structures of two PbSb₂O₆-type compounds containing titanium, CdTi₂O₄(OH)₂ and LaTiSbO₆ were refined by X-ray powder diffraction data. For both compounds structure refinements with the space group were successful and the R-factors were R_WP = 6.46% and R_P = 4.90% for CdTi₂O₄(OH)₂ and R_WP = 9.55% and R_P = 7.17% for LaTiSbO₆. These crystal structures were the same as that of the typical PbSb₂O₆-type compound in spite of the existence of protons in the interlayer or two different metal ions in the layer.     

Novel Dy-doped Ca2Gd8(SiO4)6O2 white light phosphors for Hg-free lamps application

The luminescent properties of Ca₂Gd_8(1−x)(SiO₄)₆O₂:xDy³⁺ (1% ≤ x ≤ 5%) powder crystals with oxyapatite structure were investigated under vacuum ultraviolet excitation. In the excitation spectrum, the peaks at 166 nm and 191 nm of the vacuum ultraviolet region can be assigned to the O²⁻ → Gd³⁺, and O²⁻ → Dy³⁺ charge transfer band respectively, which is consistent with the theoretical calculated value using Jφrgensen's empirical formula. While the peaks at 183 nm and 289 nm are attributed to the f-d spin-allowed transitions and the f-d spin-forbidden transitions of Dy³⁺ in the host lattice with Dorenbos's expression. According to the emission spectra, all the samples exhibited excellent white emission under 172 nm excitation and the best calculated chromaticity coordinate was 0.335, 0.338, which indicates that the Ca₂Gd₈(SiO₄)₆O₂:Dy³⁺ phosphor could be considered as a potential candidate for Hg-free lamps application.     

New substitutions and novel derivatives of the Aurivillius phases, Bi5TiNbWO15 and Bi4Ti3O12

We investigated isomorphous substitution of several metal atoms in the Aurivillius structures, Bi₅TiNbWO₁₅ and Bi₄Ti₃O₁₂, in an effort to understand structure-property correlations. Our investigations have led to the synthesis of new derivatives, Bi₄LnTiMWO₁₅ (Ln = La, Pr; M = Nb, Ta), as well as Bi₄PbNb₂WO₁₅ and Bi₃LaPbNb₂WO₁₅, that largely retain the Aurivillius (n = 1) + (n = 2) intergrowth structure of the parent oxide Bi₅TiNbWO₁₅, but characteristically tend toward a centrosymmetric/tetragonal structure for the Ln-substituted derivatives. On the other hand, coupled substitution, 2Ti^IV → M^V + Fe^III in Bi₄Ti₃O₁₂, yields new Aurivillius phases, Bi₄Ti_3−2xNb_xFe_xO₁₂ (x = 0.25, 0.50) and Bi₄Ti_3−2xTa_xFe_xO₁₂ (x = 0.25) that retain the orthorhombic noncentrosymmetric structure of the parent Bi₄Ti₃O₁₂. Two new members of this family, Bi₂Sr₂Nb₂RuO₁₂ and Bi₂SrNaNb₂RuO₁₂ that are analogous to Bi₂Sr₂Nb₂TiO₁₂, possessing tetragonal (I4/mmm) Aurivillius structure have also been synthesized.     

Improved microwave dielectric properties of B2O3-doped Nd(Co1/2Ti1/2)O3 ceramics with near zero temperature coefficient of resonant frequency

The microwave dielectric properties and the microstructures of Nd(Co_1/2Ti_1/2)O₃ ceramics prepared by conventional solid-state route have been studied. The prepared Nd(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. It is found that low-level doping of B₂O₃ (up to 0.75 wt.%) can significantly improve the density and dielectric properties of Nd(Co_1/2Ti_1/2)O₃ ceramics. Nd(Co_1/2Ti_1/2)O₃ ceramics with additives could be sintered to a theoretical density higher than 98.5% at 1320 °C. Second phases were not observed at the level of 0.25-0.75 wt.% B₂O₃ addition. The temperature coefficient of resonant frequency (τ_f) was not significantly affected, while the dielectric constants (?_r) and the unloaded quality factors Q were effectively promoted by B₂O₃ addition. At 1320 °C/4 h, Nd(Co_1/2Ti_1/2)O₃ ceramics with 0.75 wt.% B₂O₃ addition possesses a dielectric constant (?_r) of 27.2, a Q × f value of 153,000 GHz (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of 0 ppm/°C. The B₂O₃-doped Nd(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.     

Study on properties of BaxSmyTi7O20 ceramics with CaO-SiO2-B2O3 glass

The effect of CaO-SiO₂-B₂O₃ (CSB) glass addition on the sintering temperature and dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics has been investigated using X-ray diffraction, scanning electron microscopy and differential thermal analysis. The CSB glass starts to melt at about 970 °C, and a small amount of CSB glass addition to Ba_xSm_yTi₇O₂₀ ceramics can greatly decrease the sintering temperature from about 1350 to about 1260 °C, which is attributed to the formation of liquid phase. It is found that the dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics are dependent on the amount of CSB glass and the microstructures of sintered samples. The product with 5 wt% CSB glass sintered at 1260 °C is optimal in these samples based on the microstructure and the properties of sintering product, when the major phases of this material are BaSm₂Ti₄O₁₂ and BaTi₄O₉. The material possesses excellent dielectric properties: ?_r = 61, tan δ = 1.5 × 10⁻⁴ at 10 GHz, temperature coefficient of dielectric constant is −75 × 10⁻⁶ °C⁻¹.     

Crystallization and microstructure of glasses in the system Na2O/MnO/SiO2/Fe2O3

Glasses with the compositions (100 − x)(0.16Na₂O/0.10MnO/0.74SiO₂)/xFe₂O₃, (x = 5-30) and 16Na₂O/10MnO/(74 − y)SiO₂/yFe₂O₃ (y = 5-30) were studied using X-ray diffraction and scanning electron microscopy. The effect of the chemical composition and the thermal history on the phase formation and the resulting microstructure was investigated. During cooling, the precipitation of ferrimagnetic solid solutions Fe₃O₄/Mn₃O₄ was observed. These crystals show dendritic or platelet shape, whereby the platelets are ferromagnetic and the dendrites - mainly paramagnetic. The tendency towards crystallization can be suppressed by increasing the Na₂O-concentration. In contrast to glasses without manganese oxide, the precipitation of hematite is not observed. Therefore, the addition of reducing agents is not required, in order to crystallize large volume concentrations of the ferrimagnetic phase.     

Hydrothermal synthesis and magnetic property of Cu3(OH)2V2O7·nH2O

Copper vanadium oxide hydroxide hydrate (Cu₃(OH)₂V₂O₇·nH₂O) nanoparticles with mean size of about 100 nm were successfully synthesized by a simple hydrothermal method. The structure and morphology of the as-synthesized products were characterized by X-ray diffraction (XRD), Field emission scanning electron microscopy (FE-SEM), Raman spectra, and Fourier transform infrared spectra (FTIR). The composition and purity of the as-synthesized Cu₃(OH)₂V₂O₇·nH₂O nanoparticles were characterized by Energy disperse spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The magnetic property of the as-synthesized Cu₃(OH)₂V₂O₇·nH₂O nanoparticles was characterized by vibrant sample magnetometer. Magnetic hysteresis curve indicate that the as-synthesized nanoparticles are of weak ferromagnetic property at room temperature.     

Hydrothermal fabrication of various morphological α-Fe2O3 nanoparticles modified by surfactants

Two kinds of various morphological α-Fe₂O₃ nanoparticles modified by anionic surfactant (sodium dodecylsulfonate, SDS) and cationic surfactant (hexadecyipyridinium chloride, HPC), respectively, have been synthesized via hydrothermal method, using simple inorganic salt (NH₄)₃Fe(C₂O₄)₃ and alkali NaOH as starting precursors. Meanwhile, α-Fe₂O₃ nanoparticles without surfactant are also fabricated under the same conditions for comparison. The resultant products were characterized by means of Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron micrograph (TEM) combined with electron diffraction (ED) and magnetization measurements. It is interesting that the obtained α-Fe₂O₃ nanoparticles without surfactant are polyhedral with average particle size of 90 ± 35 nm; while the obtained α-Fe₂O₃ nanoparticles modified by SDS are ellipsoidal with mean particle size of major axis: ca. 420 nm; minor axis: ca. 205 nm and those modified by HPC are spherical with mean particle size of ca. 185 nm observed from TEM. In addition, magnetic hysteresis measurements reveal that the α-Fe₂O₃ nanoparticles modified by two surfactants show enhancement in coercivity (H_c) and the remanent magnetization (M_r) compared with those of the obtained α-Fe₂O₃ nanoparticles without surfactant at room temperature. The experimental results suggest that the surfactants not only significantly influence the size and shape of the particles, but also their magnetic properties.     

Preparation and photocatalytic activity of alkali titanate nano materials A2TinO2n+1 (A = Li, Na and K)

Photocatalysts nano A₂Ti_nO_2n+1 (A = Li, Na, K) were prepared successfully by novel hydrothermal synthesis process. Powders were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible (UV-vis) absorption spectra and field-emission scanning electron microscope (FE-SEM) measurements. These results showed that the compositions of lithium, sodium and potassium titanates were Li₂TiO₃, Na₂Ti₃O₇ and K₂Ti₈O₁₇, respectively. The nano crystals of Li₂TiO₃ were self-assembled as snowflakes while that of Na₂Ti₃O₇ and K₂Ti₈O₁₇ were nanorods. Photocatalytic properties of alkali titanates were also investigated. The results indicated that alkali titanates as prepared have higher photocatalytic activities compared with P25 TiO₂ in the degradation of chloroform under UV light irradiation. A combination of K₂Ti₈O₁₇ and NiO produces a photocatalyst effective for the degradation of chloroform in aqueous solution. The framework of the tunnel structure was suitable for accommodating cocatalysts such as NiO to induce a strong interaction between the active species and cocatalysts. Na₂Ti₃O₇ has high photocatalytic activity under visible-light irradiation due to its strong absorption in the visible light region. The photocatalytic properties of Li₂TiO₃ are inferior to that of Na₂Ti₃O₇ and K₂Ti₈O₁₇ due to its mono-perovskite structure.     

Vacuum ultraviolet excited photoluminescence properties of novel Na3Y9O3(BO3)8:Eu phosphor

The novel vacuum ultraviolet (VUV) excited Na₃Y₉O₃(BO₃)₈:Eu³⁺ red phosphor was synthesized and the photoluminescence (PL) properties were investigated. The phosphor showed strong VUV PL intensity, large quenching concentration (40 mol%) and good chromaticity (0.649, 0.351). The Eu³⁺-O²⁻ charge transition (CT) was observed to be at a higher energy (232 nm, 5.35 eV). The host absorption at 127-166 nm was broad and strong when monitoring the Eu³⁺ emission, which indicated that energy transfer from the host-lattice to the Eu³⁺ ions was efficient in Na₃Y₉O₃(BO₃)₈:Eu³⁺. These excellent VUV PL properties were revealed to be correlated with the unique isolated layer-type structure of Na₃Y₉O₃(BO₃)₈ host. The results showed that the Na₃Y₉O₃(BO₃)₈:Eu³⁺ would be a good candidate for VUV-excited red phosphor.     

Soft chemistry synthesis and crystal structure of MgxCu3−xV2O6(OH)4·2H2O

Mg_xCu_3−xV₂O₆(OH)₄·2H₂O (x ∼ 1), with similar crystal structure as volborthite Cu₃V₂O₇(OH)₂·2H₂O, was successfully prepared by a soft chemistry technique. The method consists of mixing magnesium nitrate and copper nitrate with a boiling solution of vanadium oxide (obtained by reacting V₂O₅ with few mL of 30 vol.% H₂O₂ followed by addition of distilled water). When ammonium hydroxide NH₄OH 10% was added (pH 7.8), a green yellowish precipitate was obtained. Using X-ray powder diffraction data, its crystal structure has been determined by Rietveld refinement. Compared to volborthite, the vanadium coordination changes from tetrahedral VO₄ to trigonal bipyramidal VO₅, and magnesium replaces copper, preferably, in the less distorted octahedron. At 300 °C, the phase formed is similar to the high pressure (HP) monoclinic Cu₃V₂O₈ phase. However at higher temperature, 600 °C, the phase obtained is different from known Cu₃V₂O₈ phases.     

Interphase synthesis of Fe3O4/CdS core-shell nanoparticles

CdS and Fe₃O₄/CdS core-shell nanoparticles were synthesized by a simple interphase method. The obtained nanoparticles were characterized by TEM, XRD and spectroscopy techniques (fluorescence and UV-vis absorption). The effects of reagent concentration on the properties of obtained nanoparticles were investigated. It was shown that the UV-vis spectra of the Fe₃O₄/CdS colloidal toluene solutions have the sharp edge at 311 nm and the long tail. The broad emission bands in the photoluminescence spectra of the Fe₃O₄/CdS organosols observed at 506, 560 and 568 nm with the increasing of cadmium oleate concentration. The thickness of CdS shell was ranged from 0.2 to 1.0 nm while the average size of the magnetite core is about 9.9 nm.     

Structure, dielectric and ferroelectric anisotropy of Sr2−xCaxBi4Ti5O18 ceramics

Sr_2−xCa_xBi₄Ti₅O₁₈(x = 0, 0.05) powders synthesized by solid state route were uniaxially pressed and sintered at 1225 °C for 2 h. The obtained dense ceramics exhibited crystallographic anisotropy with a dominant c axis parallel to the uniaxial pressing direction which was quantified in terms of the Lotgering factor. Microstructure anisotropy of both compositions (x = 0, 0.05) consisted of plate like grains exhibiting their larger surfaces mostly perpendicular to the uniaxial pressing direction. Dielectric and ferroelectric properties of Sr_2−xCa_xBi₄Ti₅O₁₈ ceramics were measured under an electric field (E) applied parallel and perpendicularly to uniaxial pressing direction. The obtained dielectric ?_R(T) and polarization (P-E) curves depended strongly on E direction thus denoting a significant effect from microstructure and crystallographic texture. Sr_2−xCa_xBi₄Ti₅O₁₈ properties were also significantly affected by Ca content (x): Curie temperature increased from 280 °C (x = 0) to 310 °C (x = 0.05) while ?_R and remnant polarization decreased for x = 0.05. The present results are discussed within the framework of the processing and crystal structure-properties relationships of Aurivillius oxides ceramics.     

Formation of NiFe2O4 nanoparticles by mechanochemical reaction

Preparation of nanosized NiFe₂O₄ particles by mechanochemical reaction(NiO+α-Fe₂O₃) and subsequent thermal treatment was investigated using X-ray diffraction (XRD). Thermal treatment of the as-milled powder at 700 °C for 1 h led to the formation of NiFe₂O₄ nanoparticles with an average crystal size of about 23 nm. Effect of thermal treatment temperature on the crystal size of the nanoparticles was studied. The mechanism of nanoparticles growth was primarily discussed. The activation energy of NiFe₂O₄ nanoparticle formation during calcination was calculated to be 16.6 kJ/mol.     

Composition dependent phase connectivity, dielectric and magnetoelectric properties of magnetoelectric composites with Pb(Mg1/3Nb2/3)0.67Ti0.33O3 as piezoelectric phase

Ferrite (Ni_0.6Co_0.4Fe₂O₄) phase, ferroelectric (Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃) phase and magnetoelectric composites of (x)Ni_0.6Co_0.4Fe₂O₄ + (1 − x)Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ with x = 0.15, 0.30 and 0.45 were prepared using solid-state reaction technique. Presence of Ni_0.6Co_0.4Fe₂O₄ and Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ was confirmed using X-ray diffraction technique. The scanning electron microscopic images were used to study the microstructure of the composites. Connectivity scheme present in the magnetoelectric (ME) composites are discussed from the microscopic images. Variation of dielectric constant and dielectric loss with temperature for all the composites was studied. Here we report the effect of Ni_0.6Co_0.4Fe₂O₄ mole fraction on connectivity schemes between Ni_0.6Co_0.4Fe₂O₄ and Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ composite. The variation of magnetoelectric voltage coefficient with dc magnetic field shows peak behaviour. The maximum value of magnetoelectric voltage coefficient of 9.47 mV/cm Oe was obtained for 0.15Ni_0.6Co_0.4Fe₂O₄ + 0.85Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ composites. Finally we have co-related the effect of Ni_0.6Co_0.4Fe₂O₄ content and dielectric properties on magnetoelectric voltage coefficient.