Natural superhydrophilicity of sol–gel derived SiO2–TiO2 composite films

Sol–gel SiO₂–TiO₂ mixed films have been deposited from a polymeric SiO₂ solution and either a polymeric TiO₂ mother solution (MS) or a derived TiO₂ crystalline suspension (CS). The chemical and structural compositions of MS and CS mixed films heat-treated at 110 or 500 °C have been investigated by Fourier transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Water contact angle measurements show that TiO₂ rich MS films exhibit photo-induced superhydrophilicity, but cannot maintain a zero contact angle in the absence of UV light. In contrast, CS mixed films exhibit a natural and persistent superhydrophilicity for a large range of compositions. Superhydrophilic properties are analyzed in terms of enhanced acidity at the SiO₂–TiO₂ interfaces and discussed with respect to the chemical and structural composition of MS and CS films.     

Effect of sputtering pressure and post-annealing on hydrophilicity of TiO2 thin films deposited by reactive magnetron sputtering

A series of TiO₂ thin films was deposited onto glass substrates without intentional heating or biasing by magnetron sputtering of a titanium target using Ar/O₂ reactive mixtures over a broad range of total sputtering pressures from 0.12 Pa to 2.24 Pa. Each of the film types was deposited by the threshold poisoned mode at a specific given oxygen flow rate monitored in-situ by optical emission spectroscopy. Both the sputtering pressure and thermal annealing are the key factors for the TiO₂ films to yield fast-response superhydrophilicity with a water contact angle of 5°. The mechanism of superhydrophilicity for the TiO₂ films deposited by high-pressure sputtering will be discussed based on empirical studies of X-ray diffractometry, high-resolution scanning microscopy and atomic force spectroscopy.     

SiO2/TiO2 multilayer films grown on cotton fibers surface at low temperature by a novel two-step process

A novel two-step process was developed to synthesize and deposit SiO₂/TiO₂ multilayer films onto the cotton fibers. In the first step, SiO₂ particles on cotton fiber surface were synthesized via tetraethoxysilane hydrolysis in the presence of cotton fibers, in order to protect the fibers against photo-catalytic decomposition by TiO₂ nanoparticles. In the second step, the growth of TiO₂ nanoparticles into the modified cotton fiber surface was carried out via a sol-gel method at the temperature as low as 100 °C. The as-obtained SiO₂/TiO₂ multilayer films coated on cotton fibers were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, atomic force microscopy and X-ray diffraction, respectively.     

Characterization of SiO2 and TiO2 films prepared using rf magnetron sputtering and their application to anti-reflection coating

Preparation of TiO₂ and SiO₂ films for optical applications was attempted using conventional rf magnetron sputtering in the sputtering ambient with various O₂/Ar+O₂ ratios and at substrate temperatures between room temperature and 400 °C. X-ray photoelectron spectroscopy (XPS) and optical spectroscopy investigations indicated that oxygen addition in the sputtering ambient was essential for growing TiO₂ films with stoichiometric compositions and good transmittance, while SiO₂ films had a stoichiometric composition of O/Si ratio=2.1-2.2 and were highly transparent in the visible wavelength region, independent of gas composition in the growing ambient. It was also identified from scanning electron microscope (SEM), atomic force microscope (AFM) and Fourier transform infrared spectroscopy (FTIR) measurements that the structural characteristics of both TiO₂ and SiO₂ films were significantly improved with O₂ addition in the sputtering ambient, showing smoother surface morphologies and higher resistances to water absorption when compared with films grown without O₂ addition. Heating of the substrate between 200 and 400 °C considerably increased the refractive index of TiO₂ layers, resulting in dense structures along with an improvement of crystallinity. For optical applications, AR coatings composed of 2-4 multi-layers on glass were designed and manufactured by stacking in turn the SiO₂ and TiO₂ films at room temperature and O₂/Ar+O₂=10%, and the performance of the produced coatings was compared with simulation results.     

Influence of SiO2 interlayer on the hydrophilicity of TiO2/SiO2/glass produced by RF-magnetron sputtering

The effect of silicon dioxide (SiO₂) on the hydrophilicity of the TiO₂ thin film is investigated. SiO₂ and TiO₂ films were deposited on the glass by RF-magnetron sputtering. Heat-treatment for 15 h at 573 K on TiO₂/glass and TiO₂/SiO₂/glass is carried out to make Na⁺-ion diffused from the glass to the TiO₂ thin film, which results in no band-gap change but instead the enhanced crystallinity of the anatase phase-TiO₂. This in turn leads to the improvement in hydrophilicity. Irrespective of the SiO₂ interlayer, the anatase phase-TiO₂ thin film with enhanced crystallinity shows outstanding super-hydrophilicity. Consequently, under the heat-treatment condition, the SiO₂ interlayer played an important role in improving the crystallinity of the anatase phase-TiO₂ rather than preventing Na⁺-ion diffusion.     

Hydrothermal growth of rutile TiO2 nanorod films on titanium substrates

Rutile TiO₂ nanorod films have been successfully prepared on titanium substrate via a hydrothermal method using Tetra-n-butyl titanate as Ti source in the presence of concentrated hydrochloric acid. The effect of Ti substrate annealing treatment and adding of additional alkali metal chlorides in hydrothermal solution on the growth of TiO₂ nanorod films has been studied using scanning electron microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and water contact angle measurement. The growth mechanism of the TiO₂ nanorods on Ti substrate has also been discussed. It has shown that the initial rutile film transformed from anatase promotes the nucleation and epitaxial growth of rutile TiO₂ nanorods. The superior wettabilities of the TiO₂ nanorods resulted from treatments of vacuum and ultraviolet show great potential for applications in orthopaedic, dental implants, and possible photocatalysis.     

Preparation and hydrophilicity of TiO2 sol-gel derived nanocomposite films modified with copper loaded TiO2 nanoparticles

In this study, TiO₂ nanocomposite films with 10 g/L of TiO₂ and copper loaded TiO₂ nanoparticles as nanofillers were deposited on the glass substrates using the sol gel dip-coating method. FE-SEM and UV-vis spectrophotometer were used to evaluate morphological and optical properties of copper loaded titania nanoparticles. In addition, XPS and water contact angle techniques were used to study the surface properties and superhydrophilicity of titania nanocomposite films, respectively. The results indicated that copper loaded TiO₂ nanoparticles had a significant effect on the hydrophilicity of nanocomposite film and maintaining it in a dark place for a long time (6.2 degree for titania nanocomposite films with copper loaded nanoparticle and 23.7 degree for nanocomposite film with titania nanoparticles).     

Hydrophilicity of anatase TiO2/Cr-doped TiO2 thin films with different band gaps

Based on the concept that the electron-hole separation effect caused by a different band-gap structure would improve its hydrophilicity, anatase-TiO₂/Cr-doped TiO₂ thin films were synthesized by DC magnetron sputtering. The optical band gaps of TiO₂ thin films decreased from 3.23 to 2.95 eV with increasing Cr-doping content. Multilayer TiO₂ thin films with different band gaps exhibited a superhydrophilicity under UV illumination. In particular, in anatase TiO₂ (3.23 eV)/4.8% Cr-doped TiO₂ (2.95 eV), the hydrophilicity, which indicated a contact angle of less than 20°, lasted for 48 h in the dark after UV illumination was discontinued. This outstanding result has rarely been reported for TiO₂ thin films, which confirmed that the prominent superhydrophilicity of anatase TiO₂/Cr-doped TiO₂/glass could be attributed to the retardation of electron-hole recombination caused by the band-gap difference.     

Photo-fixation of SO2 in nanocrystalline TiO2 films prepared by reactive DC magnetron sputtering

We report on photo-fixation of SO₂ onto nanostructured TiO₂ thin films prepared by reactive DC magnetron sputtering. The films were exposed to 50 ppm SO₂ gas mixed in synthetic air and illuminated with UV light at 298 and 473 K. The evolution of the adsorbed SO_x species was monitored by in situ Fourier transform infrared specular reflection spectroscopy. Significant photo-fixation occurred only in the presence of UV illumination. The SO₂ uptake was dramatically enhanced at elevated temperatures and then produced strongly bonded surface-coordinated SO_x complexes. The total SO_x uptake is consistent with Langmuir adsorption kinetics. The sulfur doping at saturation was estimated from X-ray photoelectron spectroscopy to be ~ 2.2 at.% at 473 K. These films were pale yellowish and had an optical absorption coefficient being ~ 3 times higher than in undoped film. The S-doped films exhibit interesting oleophobic properties, exemplified by the poor adherence of stearic acid. Our results suggest a new method for sulfur doping of TiO₂ to achieve combined anti-grease and photocatalytic properties.     

Structural and morphological properties of Fe2O3/TiO2 nanocrystals in silica matrix

We report on structural, morphological and ordering properties of Fe₂O₃/TiO₂ nanoparticles embedded in SiO₂-based multilayers. We investigated the structure of these systems by X-ray diffraction and grazing incidence small angle X-ray scattering after post-growth annealing. We found that the presence of TiO₂ promotes the growth and crystallization of the nanocrystals of Fe₂O₃. In multilayers containing both Fe₂O₃ and TiO₂, crystalline nanoparticles create partially ordered three-dimensional arrays.     

An investigation of super-hydrophilic properties of TiO2/SnO2 nano composite thin films

A sol-gel dip coating technique was used to fabricate TiO₂/SnO₂ nano composite thin films on soda-lime glass. The solutions of SnO₂ and TiO₂ were mixed with different molar ratios of SnO₂:TiO₂ as 0, 3, 4, 6, 8, 9, 10.5, 13, 15, 19.5, 25 and 28 mol.% then the films were prepared by dip coating of the glasses. The effects of SnO₂ concentration, number of coating cycles and annealing temperature on the hydrophilicity of films were studied using contact angle measurement. The films were characterized by means of scanning electron microscopy, X-ray diffraction and atomic force microscopy measurements. The nano composite thin films fabricated with 8 mol.% of SnO₂, four dip coating cycles and annealing temperature of 500 °C showed super-hydrophilicity.     

等离子体电解氧化法制备多孔TiO2/V2O5复合物膜层及其增强光催化产氢活性

较差的光催化产氢效率极大地阻碍了TiO₂光催化剂的工业化应用。为此,本文在含有NH₄VO₃的磷酸盐溶液中,采用等离子体电解氧化(PEO)法制备了多孔TiO₂/V₂O₅复合膜光催化剂,通过扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射(XRD)、X射线光电子谱(XPS)和紫外可见漫反射光谱(UV-Vis DRS)对其组成、结构及光吸收性质进行了表征,并采用气相色谱评价了薄膜催化剂的光催化产氢性能,研究了电解液中NH₄VO₃含量对膜的结构、组成和光催化产氢性能的影响。结果表明:复合膜催化剂主要由锐钛矿和金红石型TiO₂组成,具有微孔结构,V₂O₅主要以无定形形式存在于膜中,与TiO₂有很强的相互作用,影响TiO₂的晶面间距。研究发现,元素V抑制了TiO₂的结晶和金红石型TiO₂的形成,扩大了薄膜的光学吸收范围。针对Na₂S+ Na₂SO₃溶液中的光催化产氢性能的研究显示,在质量浓度为1 g/L NH₄VO₃的电解液中制备的TiO₂/V₂O₅薄膜的光催化活性最高,优于近年来报道的其他光催化剂。光催化重复实验表明,该复合膜催化剂具有较高的稳定性和较为恒定的光催化活性。     

Photoactive and self-cleaning TiO2-SiO2 thin films on 316L stainless steel

In this study, TiO₂-SiO₂ nanocomposite films with different amounts of SiO₂ were prepared by sol-gel process and were coated onto stainless steel 316L. The effect of addition of various amount of SiO₂ in the precursor solution on the photocatalysis, photo-generated hydrophilicity and self-cleaning property of TiO₂ thin films was investigated by X-ray diffraction, Fourier transform infrared spectroscopy, water contact angle measurements and UV spectroscopy. In the tested ranges of SiO₂ content and sintering temperature, the highest photocatalytic activity and self-cleaning property were observed in the 15 mol% SiO₂ sample sintered at 750 °C. Addition of less than 30 mol% SiO₂ had a suppressive effect on the transformation of anatase to rutile and on the crystal growth of anatase in the sintering heat treatment. Phase separation occurred in the composite films for SiO₂ content of 30 mol% or more.     

Superhydrophilic anatase TiO2 film with the micro- and nanometer-scale hierarchical surface structure

Nanosized anatase TiO₂ film on the ITO glass has been fabricated via spin coat process, with sodium dodecylbenzenesulfonate modified TiO₂ nanoparticles, which is synthesized by a sol-hydrothermal method, and also characterized mainly by means of field emission scanning electron microscopy (FESEM). The results show that the as-prepared anatase TiO₂ film exhibits superhydrophilic characteristic although it is not exposed to ultraviolet irradiation. The high roughness resulting from hierarchical surface structure is responsible for its superhydrophilicity. This work would provide a new route to fabricate newly nanostructured semiconductor films.     

Gas sensors with porous three-dimensional framework using TiO2/polymer double-shell hollow microsphere

The correlations between the structures and gas-sensing properties of porous thin-film gas sensors made of packed hollow spheres are investigated. For this purpose, hollow polymeric spheres were used as templates. Double-shell hollow spheres were prepared by encapsulating the polymeric hollow spheres with TiO₂ shells. Solid polymeric spheres were used as templates for comparison. Porous thin-film gas sensor with interconnected three-dimensional pores was prepared by using the TiO₂ encapsulated hollow spheres. The double-shell hollow spheres and porous titania films were characterized by XRD, BET, TEM and SEM. The gas-sensing properties of the sensors toward NO₂ depend on the type of template and the three-dimensional porous structure of the films. Using the hollow sphere template and adding precursors during the film formation procedure help to prevent the collapse of hollow sphere and form the mesopores in films after removing the template. These films show enhanced gas sensitivity when compared to TiO₂ polycrystalline films. Such improvement in sensitivity results from the porous architecture of the hollow microsphere films which not only increase the active surface area but also promotes the gas diffusion.     

Characterization of sol-gel derived TiO2/ZrO2 films and powders by Raman spectroscopy

The effect of zirconium dioxide addition on crystal structure of sol-gel TiO₂ mesoporous films and powders has been investigated by means of Raman spectroscopy, X-Ray diffraction, and Atomic force microscopy. Zirconium incorporation (up to 30 mol%) into TiO₂ lattice resulted in the formation of Ti_1 − xZr_xO₂ solid solution with anatase structure for the binary powders has been proved. Appearance of tetragonal ZrO₂ phase was observed for the samples with high zirconium content.     

Nanoporous TiO2 thin film based conductometric H2 sensor

Nanoporous titanium dioxide (TiO₂) based conductometric sensors have been fabricated and their sensitivity to hydrogen (H₂) gas has been investigated. A filtered cathodic vacuum arc (FCVA) system was used to deposit ultra-smooth Ti thin films on a transducer having patterned inter-digital gold electrodes (IDTs). Nanoporous TiO₂ films were obtained by anodization of the titanium (Ti) thin films using a neutral 0.5% (wt) NH₄F in ethylene glycol solution at 5 V for 1 h. After anodization, the films were annealed at 600 °C for 8 h to convert the remaining Ti into TiO₂. The scanning electron microscopy (SEM) images revealed that the average diameters of the nanopores are in the range of 20 to 25 nm. The sensor was exposed to different concentrations of H₂ in synthetic air at operating temperatures between 100 °C and 300 °C. The sensor responded with a highest sensitivity of 1.24 to 1% of H₂ gas at 225 °C.     

Fabrication of transparent TiO2 film with high adhesion by using self-assembly methods: Application to super-hydrophilic film

A transparent and super-hydrophilic TiO₂ film with high adhesion was prepared by simple self-assembly methods from aqueous solution at low temperature. The excellent adherence of TiO₂ films was accomplished by introducing a buffer layer with sulfonate-modified surfaces and nanoasperity. Moreover, the structure and morphology of the films were successfully controlled by deposition temperature and the pH of precursor solution. By optimizing the several parameters of solution as well as the surface functionality of the substrate, the nano-structured TiO₂ film with high adhesion showed a water contact angle of below 5° and the relative transmittance to slide glass of over 90%. The fabricated TiO₂ film deposited under the optimized condition is not removed from substrate after several Scotch tape (STT) tests and immersing into several kinds of solvent.     

Visible-light photocatalysis in nitrogen-carbon-doped TiO2 films obtained by heating TiO2 gel-film in an ionized N2 gas

To use solar irradiation or interior lighting efficiently, we sought a photocatalyst with high reactivity under visible light. Nitrogen and carbon doping TiO₂ films were obtained by heating a TiO₂ gel in an ionized N₂ gas. The as-synthesized TiO_2−x−yN_xC_y films have shown an improvement over titanium dioxide in optical absorption and photocatalytic activity such as photodegradation of methyl orange under visible light. The process of the oxygen atom substituted by nitrogen and carbon was discussed. Oxygen vacancy induced by the formation of Ti³⁺ species and nitrogen and carbon doped into substitution sites of TiO₂ have been proven to be indispensable for the enhance of photocatalytic activity, as assessed by UV-Vis Spectroscopy and X-ray photoemission spectroscopy.     

Photocatalytic properties of porous TiO2/Ag thin films

In this study, nanocrystalline TiO₂/Ag composite thin films were prepared by a sol-gel spin-coating technique. By introducing polystyrene (PS) spheres into the precursor solution, porous TiO₂/Ag thin films were prepared after calcination at a temperature of 500 °C for 4 h. Three different sizes (50, 200, and 400 nm) of PS spheres were used to prepare porous TiO₂ films. The as-prepared TiO₂ and TiO₂/Ag thin films were characterized by X-ray diffractometry (XRD) and by scanning electron microscopy to reveal structural and morphological differences. In addition, the photocatalytic properties of these films were investigated by degrading methylene blue under UV irradiation.When PS spheres of different sizes were introduced after calcination, the as-prepared TiO₂ films exhibited different porous structures. XRD results showed that all TiO₂/Ag films exhibited a major anatase phase. The photodegradation of porous TiO₂ thin films prepared with 200 nm PS spheres and doped with 1 mol% Ag exhibited the best photocatalytic efficiency where ∼ 100% methylene blue was decomposed within 8 h under UV exposure.