Hydrothermal synthesis of a nanostructured TiO<Subscript>2</Subscript>-based material in the presence of chitosan

Quasi-one-dimensional TiO₂-based nanostructures have been produced through hydrothermal treatment-without additives and in the presence of chitosan—of anatase nanopowder synthesized by an electrochemical sol-gel process. The morphology, phase composition, and structure of the hydrothermal synthesis products were studied by various physicochemical characterization techniques, including high-resolution electron microscopy, X-ray diffraction, and IR spectroscopy. The results demonstrate that the forming one-dimensional structures are isostructural with β-titanic acid, H₂Ti₃O₇. Heat treatment at t ≥ 500°C yields a mixture of sodium polytitanates, Na _y Ti _x O_{2x + 1}, with y = 0.5–2 and x = 2–5. The surface morphology and shape of the nanostructures persist up to 700°C. The key features of the formation of quasi-one-dimensional TiO₂-based structures in the presence of chitosan have been identified.     

Nanocrystalline TiO<Subscript>2</Subscript> preparation by microwave route and nature of anatase–rutile phase transition in nano TiO<Subscript>2</Subscript>

Nanopowders of TiO₂ has been prepared using a microwave irradiation-assisted route, starting from a metalorganic precursor, bis(ethyl-3-oxo-butanoato)oxotitanium (IV), [TiO(etob)₂]₂. Polyvinylpyrrolidone (PVP) was used as a capping agent. The as-prepared amorphous powders crystallize into anatase phase, when calcined. At higher calcination temperature, the rutile phase is observed to form in increasing quantities as the calcination temperature is raised. The structural and physicochemical properties were measured using XRD, FT–IR, SEM, TEM and thermal analyses. The mechanisms of formation of nano-TiO₂ from the metal–organic precursor and the irreversible phase transformation of nano TiO₂ from anatase to rutile structure at higher temperatures have been discussed. It is suggested that a unique step of initiation of transformation takes place in Ti_1/2O layers in anatase which propagates. This mechanism rationalizes several key observations associated with the anatase–rutile transformation.     

Dielectric properties of B<Subscript>2</Subscript>O<Subscript>3</Subscript> doped Sm(Co<Subscript>1/2</Subscript>Ti<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramics at microwave frequency

The microwave dielectric properties and the microstructures of Sm(Co_1/2Ti_1/2)O₃ ceramics with B₂O₃ additions (0.25 and 0.5 wt%) prepared by conventional solid-state route have been investigated. The prepared Sm(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. Doping with B₂O₃ (up to 0.5 wt%) can effectively promote the densification of Sm(Co_1/2Ti_1/2)O₃ ceramics with low sintering temperature. It is found that Sm(Co_1/2Ti_1/2)O₃ ceramics can be sintered at 1,260 °C due to the grain boundary phase effect of B₂O₃ addition. At 1,290 °C, Sm(Co_1/2Ti_1/2)O₃ ceramics with 0.5 wt% B₂O₃ addition possess a dielectric constant (ε _r) of 27.7, a Q × f value of 33,600 (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of −11.4 ppm/ °C. The B₂O₃-doped Sm(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.     

Effects of Out-of-Plane Disorder in CaFe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>AsF System

We perform oxygen doping experiments in the CaFeAsF and CaFe_0.88Co_0.12AsF compounds. In the parent compound CaFeAsF, partial replacement of F by O leads to an increase of resistivity and a weakening of spin-density wave transition, indicating that the out-of-plane disorder strongly affects the electronic and magnetic properties of the system. In the CaFe_0.88Co_0.12AsF_1−x O _x system, the doping of oxygen leads to the suppression of superconductivity, reflecting the importance of Ca–F layer disorder in this system.     

Polarization Effect in ESR of Co Doped CuGeO<Subscript>3</Subscript>

Electron spin resonance of a single crystal of CuGeO₃ doped with 2% of Co has been studied at f = 99 GHz in temperature range 1.8–50 K. Contributions to ESR absorption from Cu²⁺ chains and from Co²⁺ ions were derived. It is found that functions obtained for ESR integrated intensities: Curie-Weiss for Cu²⁺ (χCu ∼ C _Cu/(T + Θ), with Θ = 92 K) and Curie for Co²⁺ (χCo ∼ C _Co/T) are well consistent with temperature dependence of static magnetic susceptibility. Strong dependence of ESR absorption on polarization of oscillating magnetic field was discovered for Co²⁺ contribution. Polarization effect was studied for magnetic field applied along a, b and c directions. Values of g-factors of resonance lines are presented.     

Preparation of K<Subscript>2</Subscript>Ti<Subscript>6</Subscript>O<Subscript>13</Subscript>/TiO<Subscript>2</Subscript> bio-ceramic on titanium substrate by micro-arc oxidation

K₂Ti₆O₁₃/TiO₂ bio-ceramic coatings are prepared successfully by micro-arc oxidation on titanium substrate in pure KOH electrolyte solution. The coating is prepared at various applied current density (150–500 mA/cm²) and in KOH electrolyte with different concentrations (0.5–1.2 mol/L). The composition and surface morphologies of coatings are strongly dependent on the applied current density and the electrolyte concentration. On the condition of lower current density and electrolyte concentration, K₂Ti₆O₁₃ phase almost cannot be formed. The phase is mainly composed of rutile and K₂Ti₆O₁₃ with increasing current density and electrolyte concentration. The surface morphologies are composed of whiskers and porous structures. The ability of K₂Ti₆O₁₃/TiO₂ bio-ceramic films inducing apatite deposition is evaluated by soaking it in biological model fluids. The results show the K₂Ti₆O₁₃/TiO₂ bio-ceramic coatings possess excellent capability of inducing bone-like apatite to deposit.     

On the synthesis,characterization and photocatalytic applications of nanostructured TiO<Subscript>2</Subscript>

Nanocrystalline semiconducting materials are attracting much attention due to their potential applications in solar energy conversion, nonlinear optics, and heterogeneous photocatalysis. In the present investigation, we have synthesized nanostructured TiO₂ photocatalysts, which have been used in the photocatalytic degradation of phenol (one of the most common water pollutants). These catalysts have been prepared through sol-gel technique using titanium tetra-isopropoxide as a raw material for synthesis. Characterization techniques such as XRD, SEM and TEM have been employed for structural/microstructural investigations. XRD results show that the as synthesized TiO₂ nanopowder exhibit anatase phase, TiO₂. The average sizes of the TiO₂ nanopowders are ∼ 5–10 nm. The optical properties of the samples were investigated through UV-visible and fluorescence techniques. It has been observed that absorption edge corresponds to ∼ 410 nm (bandgap, ∼ 3.02 eV). The emission peak in the fluorescence spectrum at ∼ 418 nm corresponds to the bandgap energy of ∼ 2.97 eV. Concentration of phenol (initial concentration, ∼ 100 ppm) with illumination time was monitored by measuring the absorbance of pure and illuminated phenol through UV-visible spectrophotometer. Salient feature of this study relates to the fact that the present sol-gel synthesized TiO₂ nanopowders have been found to be better photocatalysts for phenol degradation than the presently employed commercial TiO₂ (P-25, Degussa) photocatalyst. Thus, whereas phenol concentration, with the presently synthesized TiO₂ nanopowders, the concentration of phenol decreases up to ∼ 32% but for commercial TiO₂ nanopowder (P-25, Degussa), it decreased only up to ∼ 25%. The improved surface area is considered as an important factor for the aforesaid decrease in phenol concentration.     

Effects of Co doping on structure and optical properties of TiO2 thin films prepared by sol-gel method

Co-doped TiO₂ thin films were synthesized on quartz substrates by sol-gel method. Atomic force microscopy results indicate that the surfaces of the Ti_1 − xCo_xO₂ (0 ≤ x ≤ 0.10) films become smooth and compact with increasing Co content. X-ray diffraction results show that all the films are rutile phase structure and Co doping leads to lattice contraction. X-ray photoelectron spectroscopy results reveal that the predominant oxidation state of Co is divalent. Peak positions of Raman-active modes (B_2g, A_1g and E_g) shift to lower frequency with increasing Co content. The refractive index n at 670 nm from transmittance spectra increases with increasing Co content. The OBG varies between 3.10 and 3.26 eV. Note that optical band gap (OBG) first increases and then decreases with increasing Co content, reaching its maximum value when x is 0.03. These results suggest that the increasing mechanism of OBG is related to the decrease of grain size, compressive stress, and reduction of rutile TiO₂, and the decreasing mechanism of OBG is involved with defect and impurity. The competition of the two mechanisms leads to the strange change of OBG.     

Synthesis,microstructure and microwave dielectric properties of Ca<Subscript>4-x</Subscript>Mg<Subscript>x</Subscript>La<Subscript>2</Subscript>Ti<Subscript>5</Subscript>O<Subscript>17</Subscript> ceramics

Ca_4-xMg_xLa₂Ti₅O₁₇ ceramics were prepared by a solid state ceramic route for x = 0, 0.5, 1, 2, 3 and 4. The structure and microstructure of the ceramics were investigated using X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. X-ray diffraction results show that the Ca_4-x Mg _x La₂Ti₅O₁₇ adopts an orthorhombic crystal structure with no secondary phase observed for x from 0 to 0.5. Secondary phase, MgTiO₃ occurs with further increasing doping level (1 ≤ x ≤ 3). When x = 4, mixture phases La_0.66TiO_2.993, MgTiO₃ and a trace of unknown phase coexist. Ca₄La₂Ti₅O₁₇ ceramic exhibits a relative permittivity (ε_r) ~ 65, quality factor (Q × f) ~13,338 GHz (at ~4.75 GHz), and temperature coefficient of resonant frequency (τ _f ) ~ 165 ppm/°C. The sintering temperature was distinctly reduced from 1,580 °C for x = 0 to 1,350 °C for x = 4. With increasing Mg content, ε_r and τ_f obviously decrease, while Q × f value initially decreases and then increases. The ceramic for x = 2 shows ε_r ~ 50, Q × f ~ 9,451 and τ _f  ~ 62.5 ppm/°C. By the complete replacement of Ca with Mg, Mg₄La₂Ti₅O₁₇ ceramic sintered at 1,350 °C for 4 h combines a high dielectric permittivity (ε _r  = 31), high quality factor (Q × f ~ 15,021) and near-zero temperature coefficient of resonant frequency (τ _f  ~ 4.0 ppm/°C). The materials are suitable for microwave applications.     

Magnetic and ferroelectric properties of SmBi<Subscript>4</Subscript>Fe<Subscript>0.5</Subscript>Co<Subscript>0.5</Subscript>Ti<Subscript>3</Subscript>O<Subscript>15</Subscript> compounds prepared with different synthesis methods

The SmBi₄Fe_0.5Co_0.5Ti₃O₁₅ compounds were prepared by the insertion of the SmFe_0.5Co_0.5O₃ into the Bi₄Ti₃O₁₂ host and the conventional solid state reaction method, respectively. X-ray diffraction analysis indicates that the conventional solid state reaction method favors the formation of a single phase four-layer Aurivillius phase of SmBi₄Fe_0.5Co_0.5Ti₃O₁₅ more easily than that prepared by the insertion method. Magnetic and ferroelectric measurements demonstrate that the samples prepared by both methods exhibit coexistence of strong ferromagnetic and weak ferroelectric behaviors at room temperature. Compared with the Bi₅FeTi₃O₁₅, the ferromagnetism of the SmBi₄Fe_0.5Co_0.5Ti₃O₁₅ was dramatically enhanced by the partial substitution of Co for Fe and Sm for Bi. The SmBi₄Fe_0.5Co_0.5Ti₃O₁₅ samples exhibit large magnetic responses (2M _r ?~?643 memu/g and coercive fields 2H _c ?~?344 Oe) at room temperature.     

Estimation of reaction conditions for synthesis of nanosized brookite-type titanium dioxide from aqueous TiOCl<Subscript>2</Subscript> solution

Ti O₂ nanoparticles with a mixture of brookite and rutile phases were prepared from aqueous TiOCl₂ solution at 80–150°C and pure rutile phase at 200°C. The volume fraction of brookite was gradually increased with increase of HCl concentration in the range of about 4.43 M to 6.28 M. The maximum volume fraction of brookite in the as-prepared TiO₂ particles was obtained when oxidation of Ti⁴⁺ to TiO₂ was completed but it was gradually decreased with increase of reaction time. The reaction time for complete oxidation of Ti^{4 +} to TiO₂ was about 15 h at 80°C, about 5 h at 100°C, about 2 h at 120°C, and about 1 h at 150°C, respectively, showing that the kinetics of oxidation is very dependent on the reaction temperature. Brookite phase was not transformed directly to rutile phase but to anatase phase by heat-treatment at about 750°C, which finally converted to rutile phase at 1100°C.     

Room Temperature Magnetism in Co-doped ZnO Nanorods

Zn_1−x Co _x O (x=0, 0.02, 0.04, 0.06, 0.08, 0.10) nanorods have been synthesized by the hydrothermal method. XRD patterns show that all samples are wurtzite structure without impurity. The magnetization measurements show that the pure ZnO is diamagnetic, while paramagnetism dominates in Zn_1−x Co _x O nanorods. Paramagnetism increases linearly with an increasing Co concentration. The magnetic moment calculated from the magnetic susceptibility is around 4 μ _B/Co, which is close to the theoretical value of Co ions with L=1.07 and S=3/2 in all Zn_1−x Co _x O nanorods, indicating the Co atoms are mostly isolated. All the samples exhibit weak ferromagnetism. However, the saturation magnetization of the ferromagnetic contribution in Zn_1−x Co _x O almost keeps constant with increasing Co concentration. We conclude that the weak ferromagnetism in Zn_1−x Co _x O might be due to the high concentration of defects.     

Electron Magnetic Resonance,Neutron Diffraction and ac Susceptibility Study of CaMn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ru{<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3</Subscript> (x ≤ 0.40) Manganite System

Electron magnetic resonance (EMR), neutron powder diffraction (NPD) and ac susceptibility techniques were employed for studying the crystallographic structure and magnetic ordering in CaMn_1−xRu_xO₃ (x ≤ 0.40) manganite system. EMR measurements were done on polycrystalline samples at 120 ≤ T ≤ 500 K. High temperature EMR spectra of pristine antiferromagnetic (AFM) CaMnO₃ show a singlet Lorentzian-like line, whose intensity diminishes, zeroing at Neel temperature T _N=120 K. Strong broadening of paramagnetic (PM) lines with increase of Ru-content (Δ H_pp ∼ 1 T for x=0.10) was found. Upon cooling low-doped (x ≤ 0.06) samples remain AFM, whereas higher doped ones (0.10 ≤ x ≤ 0.40) clearly show progressive appearance of ferromagnetic (FM) phases. Thus, EMR evidences that Ru-doping modifies both PM and AFM states and creates an inhomogeneous phase separated FM and AFM ground states at x0.06. Complementary measurements of NPD and ac susceptibility corroborate the complex character of magnetic ordering, revealed by EMR. The changes of the magnetic ordering in CaMn_1−xRu_xO₃ supposed to be solely determined by doping of Mn-sites with Ru.     

Microstructure and Optical Properties of Tantalum Modified TiO<Subscript>2</Subscript> Thin Films Prepared by the Sol–Gel Process

Tantalum doped TiO₂ thin films ((TiO₂)_1−x (Ta₂O₅) _x , x=0, 0.1%, 0.3%, 0.5%, 0.8%) were prepared on ITO-coated substrates by means of the sol–gel method and spin coating technology followed by rapid thermal annealing treatment (RTA). The effects of various processing parameters, including Ta content (x=0–0.8%) and annealing temperature, on the growth and properties of thin films were investigated. Structural characteristics by X-ray diffraction analysis indicated that the doping of Ta₂O₅ in the TiO₂ without change the anatase structure of TiO₂ thin films. The optical transmittance of (TiO₂)_1−x (Ta₂O₅) _x thin films decrease from 50% down to 20% with increasing the Ta₂O₅ concentrations from x=0.00 to x=0.8%. The absorption coefficient shows energy gap were decreased with increasing Ta₂O₅ content from 2.932 eV for x=0.00 to 2.717 eV for x=0.8%. Doping TiO₂ with Ta₂O₅ can lower its band gap and shift its optical response to the visible region.     

High-temperature oxidation behaviour of Ti<Subscript>3</Subscript>Si<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>C<Subscript>2</Subscript> in air

The oxidation behaviours of bulk Ti₃Si_(1−x)Al _x C₂ prepared by hot pressing were investigated. The results showed that the isothermal oxidation behaviour of Ti₃SiC₂ obeyed a parabolic law between 900 and 1100°C, and followed a two-step parabolic rate law between 1200°C and 1300°C. The cyclic oxidation behaviour of material is assumed to obey a three-step parabolic rate law at 1100°C and 1200°C. The calculated activation energy of isothermal oxidation is 101·43 kJ·mol⁻¹. The oxide layers consisted of a mass of α-Al₂O₃ and little TiO₂ and SiO₂ are observed on Ti₃SiC₂ as a dense and adhesive protect scale. The oxidation mechanism varies with the additive aluminum that greatly improves the oxidation resistance of Ti₃SiC₂.     

Cu doping effect on the resistive switching behaviors of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> thin films

Spin-coated Cu_xCo_1?xFe₂O₄ (x = 0, 0.2, 0.4, 0.6, and 0.8) thin films were prepared on Pt/TiO₂/SiO₂/Si substrates. Pt/Cu_xCo_1?xFe₂O₄/Pt structures were fabricated to investigate the effect of Cu doping concentration on the resistive switching behaviors. Structural and morphology characterizations revealed that Cu doping improved the crystallization of the thin films as compared to undoped CoFe₂O₄. Current–voltage characterization showed that all Cu_xCo_1?xFe₂O₄ thin films showed unipolar resistance switching, but the distribution range of the set voltage, reset voltage, and resistances were much reduced by Cu doping. Clear improvement in the stability of these parameters started to appear with x = 0.4, and the optimized performance was observed in the Pt/Cu_0.6Co_0.4Fe₂O₄/Pt structure. The improved stability of the switching parameters was attributed to the enhancement of hopping process between the Fe ions and the Cu ions in the spinel lattice. Our results indicated that appropriate adjustment of the doping elements in oxides can be a feasible approach in achieving stable resistance switching memory devices.     

Morphological and phase dependence of nanotitania materials generated under extreme pH conditions for large scale production of TiO<Subscript>2</Subscript> nanowires (basic) and nanosquares or nanrods (acidic)

The effect that the phase of the starting nanoseed titania (TiO₂), the pH of the solvent solution, and the processing methodology employed have on the properties of the resultant TiO₂ nanomaterials were explored. This led to the development of a new process to produce large-scale, phase pure, thin nanowires of TiO₂ at high pH and nanosquares at low pH. Anatase, rutile, and Degussa P25^TM TiO₂ nanoparticle starting materials (or nanoseeds) were processed in strongly basic (10 M KOH) and strongly acidic (conc. HX, where X = Cl, Br, I) solutions using solvothermal (SOLVO) and solution precipitation (SPPT) methodologies. Under basic SOLVO conditions, the nanoseeds were converted to H₂Ti₂O₅·H₂O nanowires. The SPPT basic conditions also produced the same phased nanowires for the rutile and anatase nanoseeds, while the Degussa nanomaterial yielded mixed phased [anatase:rutile (9:1)] nanowires. The SPPT method was found to produce substantially thinner nanowires in comparison to the SOLVO route, with comparable surface areas but the strong basic media led to etching of the glassware yielding HK₃Ti₄O₄(SiO₄)₃·4H₂O nanorods. Hybridization of these two processing routes led to the use of Nalgene^TM bottle as the reaction flask termed the hybrid (HYBR) route, yielding even thinner H₂Ti₂O₅·H₂O nanowires on a large-scale. Switching to a concentrated halide acid (HX, where X = Cl, Br, I) system, SOLVO, SPPT, and HYBR routes were investigated. The resultant TEM images revealed that the rutile starting material yielded short rods, whereas the anatase seeds formed square or faceted materials.     

Ferromagnetism in Electrospun Co-doped SrTiO3 Nanofibers

By employing electrospinning technique, subsequent calcination in air and annealing process in hydrogen, uniform Co-doped SrTiO₃ nanofibers with concentrations of Co between 0 and 0.20 were successfully produced. Their morphologies and detailed structures were characterized by scanning electron microscopy, transmission electron microscopy, and X-ray powder diffraction. And, the chemical states of Co were determined by X-ray photoelectron spectroscopy. It was shown that, after calcination, Co²⁺ was well incorporated into the perovskite structure of SrTiO₃, and the nanofibers possessed smooth surface with diameters of 50–100 nm. Magnetic properties of the hydrogen-annealed and -unannealed nanofibers were both measured by physical property measurement system from 50 to 300 K. It was explored that the Co addition and the hydrogen annealing process were both very important to the generation of the observed ferromagnetism in SrTi_1−x Co _x O₃:H₂ nanofibers. In hydrogen-annealed SrTi_0.80Co_0.20O₃:H₂ nanofibers, a saturation magnetization of 0.74 emu/g and an average moment of 0.122 μ_B/Co were obtained. The origins of the enhanced ferromagnetism in SrTi_1−x Co _x O₃:H₂ nanofibers were analyzed according to the chemical state of Co and the mediation of oxygen vacancies.     

Microstructure and H<Subscript>2</Subscript>S gas sensing properties of nanocrystalline perovskite-type La<Subscript>0.6</Subscript>Co<Subscript>0.4</Subscript>Mn<Subscript>0.5</Subscript>Ni<Subscript>0.5</Subscript>O<Subscript>3</Subscript>

Nanocrystalline La_1−x Co _x Mn_1−y Ni _y O₃ (x = 0.2 and 0.4; y = 0.1, 0.3, and 0.5) thick films sensors prepared by sol–gel method were studied for their H₂S gas sensitivity. The structural and morphological properties have been carried out by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Average particle size estimated from XRD and TEM analyses was observed to be 30–35 nm. The gas response characteristics were found to depend on the dopants concentration and operating temperature. The maximum H₂S gas response of pure LaMnO₃ was found to be at 300 °C. In order to improve the gas response, material doped with transition metals Co and Ni on A- and B-site, respectively. The La_0.6Co_0.4Mn_0.5Ni_0.5O₃ shows high response towards H₂S gas at an operating temperature 250 °C. The Pd-doped La_0.6Co_0.4Mn_0.5Ni_0.5O₃ sensor was found to be highly sensitive to H₂S at an operating temperature 200 °C. The gas response, selectivity, response time and recovery time were studied and discussed.     

Low-temperature sintering and microwave dielectric properties of TiO<Subscript>2</Subscript>-based LTCC materials

Temperature stable high-K LTCC material was prepared. The influence of fabrication process on the crystalline phases, microstructures and microwave dielectric properties of TiO₂-Bi₂O₃-CuO ceramics were investigated. The crystalline phases and microstructures of TiO₂-Bi₂O₃-CuO ceramics were investigated by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. It was found that rutile TiO₂ phase and Bi₂Ti₄O₁₁ phase co-existed in the TiO₂-Bi₂O₃-CuO ceramics. Separate TiO₂ grains and Bi₂Ti₄O₁₁ grains distributed uniformly in the ceramic matrix. The composition 0.92TiO₂-0.08Bi₂Ti₄O₁₁ with 2 wt% CuO addition that was sintered at 900 °C for 2 h showed high dielectric constant (ε_r ~ 81), high quality factor (Q × f ~ 3,500 GHz) and near zero temperature coefficient of resonant frequency (τ_f ~ −5.1 ppm/°C), meanwhile the compatibility test showed that it could co-fire with silver electrode. The processing-microstructure-property interrelationship was also studied.