Sol-Gel Nanosized Semiconducting Titania-Based Powders for Thick-Film Gas Sensors

Pure, 5 at%, and 10 at% Ta- or Nb-doped TiO₂ nanosized powders were prepared by the sol-gel method. The powders heated to 400°C have the crystalline anatase structure. While the pure TiO₂ powder heated to 850°C has the rutile structure, the addition of Ta and Nb inhibited the anatase-to-rutile phase transformation at this temperature. Ta was soluble in the titania lattice up to the concentration of 10 at%, while the solubility of Nb was 5 at%. Thick films were fabricated with these powders by screen printing technology and then fired at 650°C and 850°C for 1 h. SEM observations showed that the anatase-to-rutile phase transformation induces a grain growth of about one order of magnitude for pure TiO₂. The addition of Ta and Nb is effective to keep the TiO₂ grain size at the nanometric level even at 850°C. Conductance measurements showed that a good gas response is observed only for the nanostructured titania-based films. The CO response of these materials is only slightly affected by humidity.     

XAS investigation of tantalum and niobium in nanostructured TiO2 anatase

Sol-gel routes were used to prepare Ta 10 at% and Nb 5 at% and 10 at% doped titania nanosized powders. When fired between 410°C and 850°C the doped titania powders are in the anatase phase; further heating up to 1050°C is required to obtain the rutile phase. The presence of dopant atoms delays the rate of transformation as compared with pure titania powders. Doping also affects the rate of grain growth and increases the conductance response to gas. To better understand the role played by dopant atoms in inhibiting both phase transformation to rutile and grain growth, X-ray Absorption Spectroscopy measurements were performed at the L_III-L_I absorption edges of Ta and Nb K absorption edge. Analysis was restricted to the anatase phase because the transformation to rutile phase, obtained by firing at 1050°C, is accompanied by the formation of undesired Ta and Nb oxides (Ta₂O₅ and Nb₂TiO₇, respectively). Extended X-ray Absorption Fine Structure and X-ray Absorption Near-Edge Spectroscopy analysis results indicate that in nanostructured anatase both tantalum and niobium atoms substitute Ti cations with +5 valence state.     

Electrical Properties of Transparent Doped Oxide Films

In the present study n-type and p-type transparent conductive TiO₂ films were prepared by using sol-gel method. The n-type TiO₂ films were obtained by using Ti(OC₃H ₇ ⁱ )₄ solutions co-doped with Ru and Ta. The films were uniform and transparent in all the conditions, and their crystalline phases were anatase when HCl or HNO₃ was used as a catalyst. The resistivity decreased with increasing Ta content and increased with increasing Ru content. Most of the films showed resistivity minima at a heat-treatment temperature of 700°C. The lowest resistivity of 10¹ 10² cm was attained. The p-type TiO₂ films were obtained by using Ti(OC₃H ₇ ⁱ )₄ solutions co-doped with Co and Nb (Sb). The films were also uniform and transparent when AcAc was used, while samples heat-treated at 800°C became opaque when HCl was added. Rutile single phase appeared when the films were heat-treated at 700°C. Logarithmic resistivity of films co-doped with Co and Nb was directly proportional to the reciprocal absolute temperature. On the other hand, the slopes for films co-doped with Co and Sb were different below and above 200°–220°C. The activation energy at the low-temperature region is as low as 0.17 eV, and the resistivity at room temperature is 10⁴ 10⁵ cm.     

The effects of trace elements on the crystal properties of TiO2

The effects of trace element doping of TiO₂ on the crystal growth and on the anatase-to-rutile phase transformation of TiO₂ were investigated. The co-precipitation process, from sulfate solution, of doped (Cr, Fe, V, Nb, Si, P) TiO₂ was also studied. The heating temperatures were 473, 673, 873, 993, 1133 K and a higher temperature needed to achieve a rutile content of 98–99%. Traces of reduced titanium were found in freshly calcined anatase by X-ray diffraction. Pure anatase structure was found in 85% of the samples heated below 1000 K. Anatase-to-rutile transformation was accelerated by the mmol% content of Nb, Cr, Si, and Fe in TiO₂. Interaction of co-precipitated or impregnated cations was found critical in the phase transformation process. Nb retarded the crystal growth during calcination. Sulfate ions minimized the specific surface area of TiO₂ heated at low temperatures. These results of doped TiO₂ serve to promote the development of new high-technology TiO₂ products for photocatalytic purposes.     

SrBi2Nb2O9 Ferroelectric Powders and Thin Films Prepared by Sol-Gel

Pure SrBi2Nb2O9 powders and thin films were obtained using sol-gel synthesis from mixtures of niobium ethoxide, bismuth and strontium 2-ethylhexanoates. Powders crystallized for 2 hours at 700°C had grain sizes of about 100–150 nm. SrBi2Nb2O9 thin films were prepared by spin-coating a stable precursor solution onto Si/SiO2/TiO2/Pt substrates. Crystallization of pure SrBi2Nb2O9 phase occurred at about 500–550°C. Randomly oriented 0.3 m-thick crack-free films were obtained after 10 successive depositions and heating at 700°C for 2 hours. P-E hysteresis loops have confirmed the ferroelectric behavior of the films: they show a remanent polarization of 2.5 C/cm2 (5 V, 8 ms). No fatigue was observed up to 109 full switchings.     

掺杂二氧化锡的二氧化钛的光学性质及其光催化特性

二氧化钛多相催化是一种极具前途的环境污染深度净化技术。 本文以钛酸四丁酯和四氯化锡为原料,无水乙醇为溶剂,采用溶胶-凝胶法制备了掺杂二氧化锡的二氧化钛薄膜和复合氧化物粉体。通过测量薄膜的吸收光谱推算光学能隙,结果发现掺杂样品的光学能隙比纯二氧化钛样品有所变小。随着热处理温度的提高,掺杂和纯二氧化钛样品的光学能隙都略微降低。X-射线衍射分析表明,复合氧化物粉体的热处理温度对样品的晶体结构和光催化性能有重要影响。以掺杂二氧化锡5 % 摩尔比的样品与纯二氧化钛对照,500 ℃以下热处理样品以锐钛矿结构为主,600 ℃热处理样品为锐钛矿与金红石相共存,并显示了较好的光催化性能。透射电子显微镜观察显示,同样600 ℃热处理,掺杂样品要比纯二氧化钛具有更小的颗粒尺寸。在700 ℃热处理的样品中,掺杂样品只存在金红石相而纯二氧化钛样品中仍存有锐钛矿相。用阿伦尼乌斯经验关系式推测的晶粒生长的活化能,纯二氧化钛47.486 kJ.mol, 掺杂5 % 摩尔比的复合氧化物样品33.103 kJ.mol。以亚甲基蓝为降解物质,考察了掺杂量和热处理温度对样品的光催化性能。     

Synthesis of PbTiO3 ceramics using mechanical alloying and solid state sintering

The pressure-less sintering behavior of PbTiO₃ powders synthesized by mechanical alloying TiO₂ and PbO was investigated using dilatometry and Rietveld refinements of X-ray diffraction patterns. As-synthesized, the powders are nanocrystalline with a mean particle size of 20 nm. Pressure-less sintering in the range 500-1050°C gives single phase ceramics with densities of 85-90% and crystallite sizes in the range 80-400 nm. Cracking due to the paraelectric-ferroelectric phase transition was not observed in samples sintered below 700°C due to the small crystallite size whereas macroscopic cracks formed in samples sintered above 700°C. Rietveld analysis indicates the formation of Pb vacancies in samples sintered and held for 24 h at intermediate temperatures (600-1000°C) which gives some insight into the mechanism of Pb loss and second phase formation in this system.     

Phase composition and magnetic properties of niobium-iron codoped TiO2 nanoparticles synthesized in Ar/O2 radio-frequency thermal plasma

Nanoparticles of Nb⁵⁺-Fe³⁺ codoped TiO₂ with various Nb⁵⁺ concentrations (Nb/(Ti+Fe+Nb)=0-10.0 at%) and Fe³⁺ (Fe/(Ti+Fe+Nb)=0-2.0 at%) were synthesized using Ar/O₂ thermal plasma. Dopant content, chemical valence, phase identification, morphology and magnetic properties were determined using several characterization techniques, including inductively coupled plasma-optical emission spectrometer, X-ray photoelectron spectroscopy, X-ray diffraction, UV-vis diffuse reflectance spectrometer, field-emission scanning electron microscopy, transmission electron microscopy and SQUID commercial instrument. The XRD revealed that all the plasma-synthesized powders were exclusively composed of anatase as major phase and rutile. The rutile weight fraction was increased by the substitution of Fe³⁺ for Ti⁴⁺ whereas it was reduced by the Nb⁵⁺ doping. The plasma-synthesized Nb⁵⁺-Fe³⁺ codoped TiO₂ powders had intrinsic magnetic properties of strongly paramagnetic and feebly ferromagnetic at room temperature. The ferromagnetic properties gradually deteriorated as the Fe³⁺ concentration was decreased, suggesting that the ferromagnetism was predominated by the phase composition as a carrier-mediated exchange.     

On the precipitation of coherent spinel nanoparticles in Ti-doped MgO

The Mg₂TiO₄/MgO composites prepared by reactive sintering of MgO and TiO₂ powders (9:1 molar ratio) at 1600 °C and then air-cooled or further aged at 900 °C were studied by X-ray diffraction and analytical electron microscopy in order to characterize the microstructures and formation mechanism of nanosized Mg₂TiO₄ spinel precipitated from Ti-doped MgO. Expulsion of Ti⁴⁺ during cooling caused the formation of (001)-specific Guinier-Preston zone under the influence of thermal/sintering stress and then the spinel precipitates, which were about 30 nm in size and nearly spherical with {111} and {100} facets to minimize coherency strain energy and surface energy. Secondary nanosized spinel was precipitated and became site saturated during aging at 900 °C, leaving a precipitate-free zone at the grain boundaries of Ti-doped MgO. The intergranular spinel became progressively Ti-richer upon aging at 900 °C and showed 〈110〉-specific diffuse scatter intensity likely due to short-range ordering and/or onset decomposition.     

Structural Changes in Sol-Gel Derived SiO2 and TiO2 Films by Exposure to Water Vapor

Structural changes in sol-gel derived thin films by exposure to water vapor were investigated using Fourier transform infrared absorption spectroscopy, ellipsometry and x-ray diffraction. We found that SiO₂ gel films were densified with a decrease in OH groups by the exposure at 60°–180°C. The shrinkage and the peak frequency of ₄ (TO) for the exposed films were comparable to those heated in a dry atmosphere at temperatures above 500°C. However, OH groups in the films were not completely removed by the water exposure. A subsequent annealing above 300°C changed the structure of the water-exposed SiO₂ films with condensation of the remaining OH groups. Although the exposed SiO₂ gel films were amorphous, TiO₂ gel films were transformed to anatase with a decrease in OH groups by the treatments at 80°–180°C.     

Formation of Superhydrophobic-Superhydrophilic Pattern on Flowerlike Alumina Thin Film by the Sol-Gel Method

We have prepared superhydrophobic surfaces which become superhydrophilic by heat-treatment at 500°C or irradiation of UV-light. When hydrolyzed fluoroalkyltrimethoxysilane (FAS) was coated on Al₂O₃ gel film with a roughness of 20 to 50 nm, the films showed superhydrophobicity and high transparency; the contact angle for water of the film was 165° and the transmittance for the visible light was higher than 92%. When the FAS-coated thin films were heat-treated at temperatures higher than 500°C, the films became superhydrophilic; the contact angle for water on the films was smaller than 5°. Thin films of amorphous TiO₂ or anatase TiO₂ were coated between Al₂O₃ gel and FAS layer, and the contact angle for water was also about 160°. UV irradiation using high-pressure mercury lamp on these films resulted in the contact angle to be smaller than 5°. When UV light was irradiated through a photomask, superhydrophobic-superhydrophilic micropatterns applicable as a stamper for printing or a substrate of micro-optical components were successfully obtained on the films.     

NiO-SiO2 Sol-Gel Nanocomposite Films for Optical Gas Sensor

Recently nanocomposites with sensoring function are becoming a new area of interest in the field of optical gas sensor. In fact, the optical transmittance of nano-particles or thin films has been reported to be changed by atmosphere gases. In particular it was found that NiO, Co₃O₄ and Mn₃O₄ thin films showed reversible decrease in the Vis-NIR absorption due to CO.Aim of this work is the synthesis and the characterization of SiO₂ sol-gel glass films doped with NiO nanocrystals.Films of composition (100 – X)SiO₂-XNiO with X = 10, 20, 40, were obtained by mixing a matrix solution of Si(OC₂H₅)₄ (TEOS) and CH₃Si(OC₂H₅)₃ (MTES) as SiO₂ precursors, with a doping solution containing NiCl₂ as precursor for NiO particles.3-Aminopropyltriethoxysilane (3-APTES), bearing either an ammine group capable of coordinating the Ni ions and hydrolysable siloxane groups for anchoring the metal complex moiety to the silicate matrix, was used as bifunctional ligand.Transmission electron microscopy micrographs showed a uniform distribution of round shaped nanoparticles in film heated at 500°C with a mean diameter of 2.5 nm.The film composition evaluated from Rutherford backscattering spectrometry was in good agreement with the nominal one. As expected the density of the films heated at 1000°C is much higher than the density of the film heated at 500°C due to a residual porosity. Fourier transform infrared spectra also confirmed the presence of residual porosity in the films heated at 500°C.     

Synthesis of Spherical Titanium Dioxide Particles by Homogeneous Precipitation in Acetone Solution

Titania powders were synthesized by thermal hydrolysis of titanium tetrachloride in a mixed solvent was studied. The dielectric constant was tuned by regulating the acetone/water volume ratio (R/H ratio) and temperature of the solvent. Hydroxypropyl cellulose (HPC) was used as a steric dispersant. The synthesis were carried out at R/H ratios of 0–4, temperatures of 70–90°C, TiCl₄ concentrations of 0.05–0.2 M, HPC concentrations of 0–5 × 10^–3 g/cm³, and synthesis times of 15–60 min. The TiO₂ particles obtained at an R/H ratio of 0, i.e., pure water system, were fine and agglomerated. In contrast, the TiO₂ particles prepared at an R/H ratio of 3 were uniform and spherical. The TiO₂ particle size increased with increasing TiCl₄ concentration. The synthesis temperature did not influence the particle size, but greatly influenced the morphologyof the TiO₂. Adding HPC to the solution yielded more uniform and spherical particles. In addition, the synthesis time should be longer than 30 min to obtain the most uniform and spherical particles. The dielectric constant of the acetone-water mixed solvent at 28 gave the most uniform and spherical TiO₂ particles. The powders prepared at the condition of 0.1 M TiCl₄, R/H ratio of 3, HPC concentration of 0.001 g/cm³, temperature of 70°C, and synthesis time of 1 h exhibited the most uniform and spherical morphology. The as-synthesized powder was anatase and retained the phase below 400°C. It transformed to the rutile phase after calcination at 700°C.     

Crystallization Processes in Composite Biomaterials

The crystallization processes in composite biomaterials containing fluorapatite (FA) and gel glasses (GG) have been investigated. Using the sol-gel method three gel-glasses have been synthesized: ZnO·SiO₂, ZnO·Al₂O₃·2SiO₂ and ZnO·CaO·2SiO₂. The composites have been prepared from GG and FA in different mole ratios and each of them treated at 950°C, 1050°C, 1150°C and 1250°C. From the XRD analysis of the composites it has been established that fluorapatite is present as a major crystalline phase. The XRD patterns and the IR spectra of the pure GG systems have been studied at 200°C, 600°C and 800°C. The surface of the samples has been analyzed before and after the in vitro experiments using SEM. An amorphous layer has been observed on the surface of each of the treated samples. The element concentration and the solubility of the samples have been analyzed after the in vitro experiments by Atomic Absorption Spectroscopy (AAS).     

Preparation and Characterization of Titania Thin Films from Aqueous Solutions

Dip- or spin-coating and characterization of titania (TiO₂) thin films from various aqueous solutions have been studied. The aqueous titanium solutions mainly used in this study were halogen- and chelate-free solutions with the concentrations up to 1.4 M derived from titanium isopropoxide (TIP) with tetramethylammonium hydroxide (TMAOH) or some alkylamines, while aqueous and alcoholic solutions containing titanium atoms stabilized chelating ligands were examined for comparison. The TiO₂ films prepared from the TIP-TMAOH solution were already crystallized at 350°C to anatase form and those formed at 600°C had high transparency and refractive indices of 2.40. No carbon residue in the film prepared at 400°C was detected by XPS. The pure anatase form was sustained up to 850°C. Interestingly, it was found that the (004) preferentially oriented anatase films were obtained from TIP-lactic acid (LA) system until 700°C. The solutions containing citric acid (CA) or alkanolamines yielded anatase and rutile form fired at the temperatures equal to or higher than 600°C. Carbon residue was detected in the film fired at 400°C. The film thickness monotonically decreased from the upper to the bottom ends of the substrate. However, it was found that the thickness uniformity was drastically improved by an addition of sucrose to the aqueous solutions. The effects of the solution composition and polyhydroxy compounds on the crystal modifications of formed films and the film uniformity are discussed.     

Effect of α-Hydroxyketones as Chelate Ligands on Dip-Coating of Zirconia Thin Films

The stabilization effects of -hydroxyketones such as acetoin, acetol, and their imine derivatives of monoethanolamine (MEA) on the 2-propanol solution of metal alkoxides (Al, Ti, Zr, Nb and Ta) were investigated. The hydroxyketones, especially acetoin which has a moderate boiling point around 150°C, were found to have a stabilization effect on the alkoxides of Ti^IV, Nb^V and Ta^V already in their molar ratios of 2, while the Zr^IV alkoxide was stabilized at the molar ratio of 4. By sol-gel processing using this acetoin-stabilized solution, crystallized ZrO₂ thin films could be prepared at temperatures as low as 400°C, which was lower than that from a diethanolamine (DEA)-stabilized precursor (450°C). The films prepared in this study showed a high transparency (more than 90%, UV-VIS spectroscopy), suggesting that the use of chelate ligands with low boiling points is a good way to lower the crystallization temperature of sol-gel-derived ZrO₂ thin films. The Zr complexes of the imines made by the reaction between the hydroxyketones and MEA were stable and photosensitive (<500 nm), making it possible to pattern ZrO₂ films by photo-irradiation of their gel films.     

The effect of F-doping and temperature on the structural and textural evolution of mesoporous TiO2 powders

Mesoporous F⁻-doped TiO₂ powders were prepared by hydrolysis of titanium tetraisopropoxide (TTIP) in a mixed NH₄F-H₂O solution. Effects of F⁻ ion content and calcination temperatures on the phase composition and porosity of mesoporous titania were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and BET surface areas. The results showed the BET surface area (S_BET) of the pure and doped powders dried at 100°C ranged from 260 to 310 m²/g as determined by nitrogen adsorption. With increasing calcination temperatures, the S_BET values of the calcined titania powders decreased due to the increase in crystalline size. The pore size distribution was bimodal with fine intra-particle pore and larger inter-particle pore as determined by nitrogen adsorption isotherms. The peak pore diameter of intra-particle pore increases with increasing F⁻ ion content. At 700°C, all the titania powders exhibit monomodal pore size distributions due to the complete collapse of the intra-particle pores. The crystallization of anatase was obviously enhanced due to F⁻-doping at 400°C and 500°C. Moreover, with increasing F⁻ ion concent, F⁻ ions not only suppressed the formation of brookite phase at low temperature, but also prevented phase transition of anatase to rutile at high temperature.     

Effects of hydrothermal post-treatment on microstructures and morphology of titanate nanoribbons

Titanate nanoribbons were prepared via a hydrothermal treatment of rutile-type TiO₂ powders in a 10 M NaOH solution at 200 °C for 48 h. The as-prepared titanate nanoribbons were then hydrothermally post-treated at 150 °C for 12-36 h. The titanate nanoribbons before and after hydrothermal post-treatment were characterized with FESEM, XRD, TEM, UV-VIS and nitrogen adsorption-desorption isotherms. The results showed that the hydrothermal post-treatment not only promoted the phase transformation from titanate to anatase TiO₂, but also was beneficial to the removal of Na⁺ ions remained in the titanate nanoribbons. After hydrothermal post-treatment, the TiO₂ samples retained the one-dimensional structure feature of the titanate nanoribbons and showed an obvious increase in the specific surface area and the pore volume.     

Crystallization Behavior of SiO2-TiO2 Sol-Gel Thin Films

The aim of this work was to investigate the crystallization behavior of thin films of SiO₂−TiO₂ made by the sol-gel process as function of the TiO₂ content and the temperature and time of heat treatment. Precursor solutions were prepared by hydrolysis of TEOS (tetraethoxysilane) and TPOT (titaniums tetraisopropoxide). Multilayer films were spun on single crystal silicon wafers. The compositions studied were (on a molar percentage basis) 20TiO₂−80SiO₂, 30TiO₂−70SiO₂, 40TiO₂−60SiO₂ and pure TiO₂. The films were heat treated at different temperatures between 300°C and 1200°C, for different periods of time (30 s-90 h). The crystallization kinetics were followed by micro-Raman spectrometry. Grazing incidence X-ray diffraction showed that the films crystallized into one or both of two crystalline phase of TiO₂: anatase and rutile (for pure TiO₂ only). The volume fractions of the crystalline phase varied from very low values (<1%), up to 100%, for a TiO₂ sample heat treated at 800°C for 8 hours. The results show that the volume fraction of crystalline phase is strongly influenced by the heat treatment temperature and also, to a smaller extent, by the heat treatment time. The most important parameter, however, is the composition of the films: the higher their TiO₂ concentration, the lower is the crystallization temperature and the larger is the crystallized fraction.     

Titania-lanthanum phosphate photoactive and hydrophobic new generation catalyst

Titania-lanthanum phosphate nanocomposites with multifunctional properties have been synthesized by aqueous sol-gel method. The precursor sols with varying TiO₂:LaPO₄ ratios were applied as thin coating on glass substrates in order to be transparent, hydrophobic, photocatalytically active coatings. The phase compositions of the composite powders were identified by powder X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM). The anatase phase of TiO₂ in TiO₂-LaPO₄ composite precursors was found to be stable even on annealing at 800 °C. The glass substrates, coated with TL1 (TiO₂-LaPO₄ composition with 1 mol% LaPO₄) and TL50 (composite precursor containing TiO₂ and LaPO₄ with molar ratio 1:1) sols and annealed at 400 °C, produced contact angles of 74° and 92°, respectively, though it is only 62° for pure TiO₂ coating. The glass substrates, coated with TL50 sol, produced surfaces with relatively high roughness and uneven morphology. The TL1 material, annealed at 800 °C, has shown the highest UV photoactivity with an apparent rate constant, k_app=24×10⁻³ min⁻¹, which is over five times higher than that observed with standard Hombikat UV 100 (k_app=4×10⁻³ min⁻¹). The photoactivity combined with a moderate contact angle (85.3°) shows that this material has a promise as an efficient self-cleaning precursor.