Comment on: Preparation,microstructure, and electrorheological property of nano-sized TiO<Subscript>2</Subscript> particle materials doped with metal oxides

We comment on the shear stresses of recently reported Na-doped, Zr-doped, Al-doped, and Ce-doped TiO₂-based electrorheological (ER) suspensions under applied electric strengths. Using deduced critical electric-field strength and additional scaled parameter, we found that the shear stresses could be analyzed using the universal yield stress equation, collapsing the data of Na-doped, Zr-doped, Al-doped, and Ce-doped TiO₂ ER fluids onto a single curve     

IR protection property and color performance of TiO<Subscript>2</Subscript>/Cu/TiO<Subscript>2</Subscript> coated polyester fabrics

Both humans and objects can emit infrared (IR) wavelengths which generate thermal emissions that can be detected with an IR camera. Therefore, highly IR reflective materials have been the subject of interest recently, for example, in achieving IR stealth. In this work, IR reflective coatings on polyester fabric in the form of a titanium dioxide/copper/titanium dioxide (TiO₂/Cu/TiO₂; TCT) sandwich-like structure are fabricated by using magnetron sputtering. The coated fabric samples are then examined by using an energy dispersive X-ray detector, a scanning electron microscope and an X-ray diffractometer. The reflection of IR wavelengths which range from 8 to 14 µm of the TCT coated fabric is evaluated. The bending stiffness, and mechanical and adhesion strengths of the coated fabric samples are also investigated. The results show that the TCT sandwich-like structure on the polyester fabric sputtered for 30 min with Cu which results in a Cu film of 200 nm in thickness is observed to have the maximum reflection of IR wavelengths. The color of the TCT coated polyester fabric samples sputtered for 5, 10, 20, and 30 min with Cu is green, yellow, brown and purple, respectively. The TCT coated fabric therefore has potential applications as IR protection textiles for military purposes.     

Redox processes in fine-particle TiO<Subscript>2</Subscript>-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> oxides

We have studied the stability of the Cr⁶⁺ ion in fine-particle TiO₂-Cr₂O₃ oxides during storage after calcination in air. The results indicate that, during storage under normal conditions for 720 days, Cr⁶⁺ is reduced to Cr³⁺. The redox process is due to partial surface hydration of the Cr₂O₃ and TiO₂ crystallites.     

Preparation and characterization of novel yellow pigments: hollow TiO<Subscript>2</Subscript> spheres doped with cerium

Ce-doped TiO₂ hollow yellow pigment particles were synthesized by coupling template-directed method with Pechini sol–gel process. The effects of water content, ethanol/acetonitrile volume ratio and tetrabutyl orthotitanate concentration, on the fabrication of PS@TiO₂ composite particles (the key intermediate product) were investigated and the final pigments were characterized in detail by X-ray diffraction, transmission electron microscopy, scanning electron microscope, X-ray photoelectron spectroscopy, and UV–vis diffuse reflection. The results show that the optimal water content and ethanol/acetonitrile volume ratio are 0.09 mol dm⁻³ and 3:1, respectively, for the construction of neat PS@TiO₂ core–shell structure without secondary titania particles, and that the damage of hollow spheres can be avoided by increasing the shell thickness, and that the prepared hollow spheres were well-crystallised with anatase phase TiO₂ and cubic CeO₂. Owing to the intrinsic yellow color and lower density, the as-prepared hollow pigments can be expected to be used for color electronic paper display.     

Effects of NiNb<Subscript>2</Subscript>O<Subscript>6</Subscript> doping on dielectric property,microstructure and energy storage behavior of Sr<Subscript>0.97</Subscript>La<Subscript>0.02</Subscript>TiO<Subscript>3</Subscript> ceramics

Sr_0.97La_0.02TiO₃ ceramics with samll amounts of NiNb₂O₆ additives were prepared by the traditional solid state sintering method, and the phase purity, microstructure, dielectric properties and energy storage behavior of the NiNb₂O₆-added Sr_0.97La_0.02TiO₃ ceramics were investigated. The results show that the grain size of the ceramics firstly decreases and then increases with increasing NiNb₂O₆ concentration. The average grain size reaches 0.55 um for the sample with 4.5 wt% NiNb₂O₆. Moreover, impedance spectroscopy (IS) analysis was employed to study the electrical conductive behavior of NiNb₂O₆-doped Sr_0.97La_0.02TiO₃ ceramics. IS results reveale that the NiNb₂O₆-doped Sr_0.97La_0.02TiO₃ ceramic has large R _gb /(R _gb  + R _g ) ratios due to the decreased grain sizes. The breakdown strength is notably improved, and the highest breakdown strength of 324 kV/cm can be achieved for the sample with 4.5 wt% NiNb₂O₆ additive. The Sr_0.97La_0.02TiO₃ sample with 4.5 wt% NiNb₂O₆ possesses the maximum theoretical energy density of 1.36 J/cm³, which is about 2 times higher than that of pure SrTiO₃ in the literature. And its energy storage efficiency reaches 91.4 % under applied electric field of 80 kV/cm. This study provides the NiNb₂O₆ added ceramic as an attractive candidate for making high-energy density capacitors.     

Ferroin adsorption on TiO<Subscript>2</Subscript>-based photocatalytic materials

We have studied ferroin adsorption on photocatalytically active nanocomposites based on TiO₂ doped with Fe³⁺, Nb⁵⁺, or W⁶⁺. The results demonstrate that the mass of an adsorbed organic substance correlates with the photocatalytic activity of the photocatalysts. High-temperature heat treatment of the nanocomposites increases manyfold the mass of an organic substance adsorbed from an aqueous solution for unit free surface area of the photocatalyst.     

Preparation of anatase F doped TiO<Subscript>2</Subscript> sol and its performance for photodegradation of formaldehyde

Anatase fluoride doped TiO₂ sol (F-TiO₂) catalyst was prepared by a modified sol-gel hydrothermal method, using tetra butyl titanate as a precursor. The influences of F doping, temperature of hydrothermal, values of medium pH on the morphology and crystallization were studied. The microstructure and morphology of sol sample were characterized by XRD, TEM, FTIR, UV–Vis–DRS, particle size distribution (PSD) and XPS. The results showed that F-TiO₂ particles in sol were spherical and partly crystallized to anatase structure, and dispersed in the aqueous medium homogeneously and that the average particle size was ca. 10.5 nm calculated from XRD and TEM results. It was also found that the addition of fluorine could improve the crystallization and adsorption of particles significantly, the photocatalytic activity for decomposition of formaldehyde were enhanced remarkably with the doping of fluorine. Possible mechanism of anatase F-TiO₂ formed under hydrothermal conditions was discussed.     

Preparation and photoelectrochemical characterization of WO<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanotube array electrode

WO₃/TiO₂ nanotube array electrode was fabricated by incorporating WO₃ with TiO₂ nanotube array via a wet impregnation method using ammonium tungstate as the precursor. TiO₂ and WO₃/TiO₂ nanotube arrays were characterized by field emission scanning electron microscopy, X-ray diffraction, and energy dispersive X-ray analysis. In order to characterize the photoelectrochemical properties of WO₃/TiO₂ electrode, electrochemical impedance spectroscopy, and steady-state photocurrent (i _ss) measurement at a controlled potential were performed in the supporting electrolyte containing different concentrations of glucose. The photoelectrochemical characterization results reveal that WO₃/TiO₂ nanotube array electrode possesses a much higher separation efficiency of the photogenerated electron–hole pairs and could generate more photoholes on the electrode surface compared with the pure TiO₂ nanotube array electrode. The i _ss for glucose oxidation at WO₃/TiO₂ nanotube array electrode is much higher than that at the pure TiO₂ nanotube array electrode.     

Preparation of lanthanum-doped TiO<Subscript>2</Subscript> photocatalysts by coprecipitation

The lanthanum-doped TiO₂ (La³⁺-TiO₂) photocatalysts were prepared by coprecipitation and sol–gel methods. Rhodamine B was used as a model chemical in this work to evaluate the photocatalytic activity of the catalyst samples. The optimum catalyst samples were characterized by XRD, N₂ adsorption–desorption measurement, SEM and electron probe microanalyses to find their differences in physical and chemical properties. The experimental results showed that the La³⁺-TiO₂ catalysts prepared by coprecipitation exhibited obviously higher photocatalytic activities as compared with that prepared by the conventional sol–gel process. The optimum photocatalysts prepared by the coprecipitation and sol–gel process have similar adsorption equilibrium constants in Rhodamine B solution and particle size distribution in water medium although there are larger differences in their surface area, morphology and pore size distribution. The pores in the sol-gel prepared catalysts are in the range of mesopores (2–50 nm), whereas the pores in the coprecipitation prepared catalysts consist of bigger mesopores and macropores (>50 nm). The morphology of the primary particles and agglomerates of the La³⁺-TiO₂ catalyst powders was affected by doping processes. The inhibition effect of lanthanum doping on the phase transformation is greater in the coprecipitation process than in the sol–gel process, which could be related with the different amount of Ti–O–La bonds in the precursors. This finding could be used for preparing the anatase La³⁺-TiO₂ catalysts with more regular crystal structure through a higher heat treatment temperature. The optimum amount of lanthanum doping is ca. 1.0 wt.% and the surface atomic ratio of [O]/[Ti] is ca. 2.49 for 1.0 wt.% La³⁺-TiO₂ catalysts prepared by the two processes. The obviously higher photocatalytic activity of the La³⁺-TiO₂ samples prepared by the coprecipitation could be mainly attributed to their more regular anatase structure and more proper surface chemical state of Ti³⁺ species. The optimum preparation conditions are 1.0 wt.% doping amount of lanthanum ions, calcination temperature 800 °C and calcination time 2 h using the coprecipitation process. As compared with the sol-gel process, the coprecipitation process used relatively cheap inorganic raw materials and a simple process without organic solvents. Therefore, the coprecipitation method provides a potential alternative in realizing large scale production.     

A nitrogen doped TiO<Subscript>2</Subscript> layer on Ti metal for the enhanced formation of apatite

Biomedical titanium metals subjected to gas under precisely regulated oxygen partial pressures (P_O2) from 10⁻¹⁸ to 10⁵ Pa at 973 K for 1 h were soaked in a simulated body fluid (SBF), whose ion concentrations were nearly equal to those of human blood plasma, at 36.5°C for up to 7 days. The effect of oxygen partial pressures on apatite formation was assessed using X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) measurements. After heating, the weight of the oxide layer (mainly TiO₂) formed on the titanium metal was found to increase with increased oxygen partial pressure. Nitrogen (N)-doped TiO₂ (Interstitial N) was formed under a P_O2 of 10⁻¹⁴ Pa. At lower P_O2 (10⁻¹⁸ Pa), only a titanium nitride layer (TiN and Ti₂N) was formed. After soaking in SBF, apatite was detected on heat-treated titanium metal samples. The most apatite was formed, based on the growth rate calculated from the apatite coverage ratio, on the titanium metal heated under a P_O2 of 10⁻¹⁴ Pa, followed by the sample heated under a P_O2 of 10 and 10⁴ Pa (in N₂). The titanium metal heated under a P_O2 of 10⁵ Pa (in O₂) experienced far less apatite formation than the former three titanium samples. Similarly, very little weight change was observed for the titanium metal heated under a P_O2 of 10⁻¹⁸ Pa (in N₂). During the experimental observation period (5 days, 36.5°C, SBF), the following relationship held: The growth rate of apatite decreased in the order P_O2 of 10⁻¹⁴ Pa > P_O2 of 10 Pa ≥ P_O2 of 10⁴ Pa > P_O2 of 10⁵ Pa > > P_O2 of 10⁻¹⁸ Pa. These results suggest that N-doped TiO₂ (Interstitial N) strongly induces apatite formation but samples coated only with titanium nitride do not. Thus, controlling the formation of N-doped TiO₂ is expected to improve the bioactivity of biomedical titanium metal.     

Production and characterization of metastable Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript> ceramic materials

Producing nanostructured materials through metastable phases is interesting in the field of ceramic materials. Metastable phases can be obtained by the Atmospheric Plasma Spray (APS) technique which, is a well-known technique to produce coatings. The initial powders are melted during the spraying obtaining a homogenized phase due to their solubility in the liquid state. Afterwards, the molten droplets are quenched in a cooled medium, producing the sought metastable phases. Finally, during material consolidation, the metastable structure evolves due to a dual structure. A suppression of the grain growth is produced as a consequence of the immiscibility of both phases in the solid state. Due to their small grain size and uniform structure, these nanostructured materials exhibit very interesting properties such as higher hardness and toughness. The aim of this research has been to produce nanostructured Al₂O₃–TiO₂ ceramic powders through APS + quenching route, starting from commercially available micron-sized powders. A complete characterization of the obtained structures using XRD, SEM, FESEM and EDS has been carried out in the Thermal Spray Center (CPT) of the University of Barcelona.     

Preparation and characterisation of nanostructural TiO<Subscript>2</Subscript>–Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> binary oxides with high surface area derived form particulate sol–gel route

Nanostructured and nanoporous TiO₂–Ga₂O₃ films and powders with various Ti:Ga atomic ratios and high specific surface area (SSA) have been prepared by a new straightforward particulate sol–gel route. Titanium isopropoxide and gallium (III) nitrate hydrate were used as precursors and hydroxypropyl cellulose (HPC) was used as a polymeric fugitive agent (PFA) in order to increase the SSA. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) revealed that powders contained both rhombohedral α-Ga₂O₃ and monoclinic β-Ga₂O₃ phases, as well as anatase and rutile. It was observed that the Ga₂O₃ formed from the nitrate precursor retarded anatase-to-rutile transformation. Furthermore, transmission electron microscope (TEM) analysis also showed that Ga₂O₃ hindered the crystallisation and crystal growth of powders. SSA of powders, as measured by Brunauer–Emmett–Teller (BET) analysis, was enhanced by introducing Ga₂O₃. Ti:Ga = 50:50 (at%/at%) binary oxide annealed at 500 °C produced the smallest crystallite size (2 nm), the smallest grain size (18 nm), the highest SSA (327.8 m²/g) and the highest roughness. Ti:Ga = 25:75 (at%/at%) annealed at 800 °C showed the smallest crystallite size (2.4 nm) with 32 nm average grain size and 40.8 m²/g surface area. Ti:Ga = 75:25 (at%/at%) annealed at 800 °C had the highest SSA (57.4 m²/g) with 4.4 nm average crystallite size and 32 nm average grain size. One of the smallest crystallite size and one of the highest SSA reported in the literature is obtained, and they can be used in many applications in areas from optical electronics to gas sensors.     

Fabrication and properties of SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> composites

Composites in the form of precipitated powders, hybrid xerogels, and SiO₂ core/TiO₂ shell particles have been produced via hydrolysis of precursors (alkoxides and inorganic derivatives of titanium and silicon) and have been characterized by differential thermal analysis, X-ray diffraction, adsorption measurements, and macroelectrophoresis. The results demonstrate that heat treatment of the composites leads to crystallization of the titanium-containing component and, accordingly, reduces their specific surface area. Hydrothermal treatment enables the fabrication of materials in which TiO₂ nanocrystals are evenly distributed over an amorphous SiO₂ matrix.     

Electrical and optical properties of TiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript>:Fe thin films

TiO₂ and TiO₂:Fe thin films have been grown by electron beam evaporation and the influence of doping and heat treatment on their electrical and optical properties has been studied.     

Preparation of rutile (TiO<Subscript>2</Subscript>) nanostructured materials at low temperature from TiCl<Subscript>4</Subscript> aqueous solution

The synthesis of rutile (TiO₂) nanostructured materials at low temperature from TiCl₄ aqueous solution was described. TiO₂ coatings on polystyrene (PS) particles were prepared by layer-by-layer assembly technique. The samples were characterized by DTA-TG, SEM, XPS, TEM and XRD techniques. The experimental results showed that pure rutile-TiO₂ coatings with nanocrystal structure were synthesized at 100 °C. On the surface of PS particles, sphere-type TiO₂ coatings exhibited uniform shape and a narrow size distribution. The amount of TO₂ (wt%) and shell thickness of particles increased with the adding of coating layers. Hollow TiO₂ spheres were obtained by calcination at 450 °C. TiO₂/PS with 2 coating layers showed higher degradation rate. The photocatalytic activity of hollow TiO₂ spheres was higher than that of TiO₂/PS.     

Oxalic acid assisted hydrothermal synthesis and optical absorption property of WO<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanocomposites

The WO₃/TiO₂ nanocomposites were successfully prepared via a facile oxalic acid assisted hydrothermal process. The oxalic acid played a vital role on the preparation of WO₃/TiO₂ nanocomposites. Notably, it has been observed that the nanocomposites exhibited the wider absorption edge, and the higher photocatalytic activity, compared with pure TiO₂. In addition, the photocatalytic mechanism was proposed, and it elaborated that WO₃/TiO₂ nanocomposite promoted the separation of the photoproduction carriers, and improved photocatalytic activity. The WO₃/TiO₂ nanocomposite may have a potential application as a UV–visible photocatalyst.     

SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> fibers from titanium-modified polycarbosilane

We developed a process for preparing SiO₂/TiO₂ fibers by means of precursor transformation method. After mixing PCS and titanium alkoxide, continuous SiO₂/TiO₂ fibers were fabricated by the thermal decomposition of titanium-modified PCS (PTC) precursor. The tensile strength and diameter of SiO₂/TiO₂ fibers are 2.0 GPa, 13 μm, respectively. Based on X-ray diffraction (XRD), scanning electron microscopy (SEM), and high resolution transmission electron microscopy (HRTEM) measurements, the microstructure of the SiO₂/TiO₂ fibers is described as anatase–TiO₂ nanocrystallites with the mean size of ~10 nm embedded in an amorphous silica continuous phase.     

Occurrence and stability of ferromagnetism in chemically synthesized cobalt doped TiO<Subscript>2</Subscript>

We report the development of ferromagnetism in ∼30 nm sized well-characterized Ti_1−x Co _x O₂ powders with x = 0.00015–0.006 and its absence for x > 0.006. In addition, these studies show the effect of Co doping on the structural stability and anatase to rutile phase transformation. X-ray diffraction data of samples synthesized by a wet chemical method and annealed at 450 °C indicate a limited solubility of ∼1.2% for Co in the anatase TiO₂ matrix, and with further increase, the CoTiO₃ phase is formed along with increased presence of rutile TiO₂. The bandgap (∼3.23 eV) of the anatase TiO₂ remained almost unchanged for x < 0.006, but decreased rapidly for x ≥ 0.006 approaching 2.8 eV for x = 0.03. The magnetic data from Ti_1−x Co _x O₂ samples with x = 0.006 showed a coercivity H _c ∼ 150 Oe and a weak magnetic moment of 0.2 μ_B/ion at 300 K. The ferromagnetism of Ti_0.994Co_0.006O₂ with open hysteresis loops continue up to a high superparamagnetic blocking temperature T _B ∼ 675 K, above which a superparamagnetic behavior was observed. Systematic changes in the structural, magnetic and optical properties suggest that Co doping is an excellent method to tailor the physical properties of TiO₂ nanoparticles.     

Preparation of microwave dielectric,Sn<Subscript>0.2</Subscript>Zr<Subscript>0.8</Subscript>TiO<Subscript>4</Subscript>

A simple coprecipitation technique is described for the preparation of tin substituted zirconium titanate ceramic powders.     

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.