Electrophoretic deposition of Sn-doped TiO<Subscript>2</Subscript> nanoparticles and its optical and photocatalytic properties

In this research, Sn-doped TiO₂ (Sn–TiO₂) nanoparticles were synthesized by a simple sol–gel method. The structure and composition of the as-prepared sample were investigated using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and ultraviolet–visible absorption spectroscopy. Electrophoretic deposition (EPD) technique was used to deposit thin films of Sn–TiO₂ on 316L stainless steel (316L SS) substrate. In order to achieve a fine and high-quality layer on the electrode surface, N-phenyl-p-phenylenediamine (NPPDA) was used as a new dispersant and charging agent in ethanolic suspensions. Based on zeta potential and conductivity measurements of the suspensions, an optimum concentration of the NPPDA dispersant was found to be 3.0 g l^?1. The in-situ EPD kinetics was also studied. The prepared Sn–TiO₂ film was used for the photodegradation of methylene blue (MB) under UV, visible and sun lights. The results revealed that the Sn–TiO₂ film could be able to degrade the MB under sunlight. The calculated degradations were 44, 65, and 73% after 2, 4 and 5 h, respectively. The relation between \(\ln \left( {\frac{{{{\text{A}}_0}}}{{\text{A}}}} \right)\) and time was linear, so it was proved that the photocatalytic degradation of MB can be characterized by pseudo-first order reaction kinetics.     

Fabrication of SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> double layer thin films with self-cleaning and photocatalytic properties

Transparent antireflective SiO₂/TiO₂ double layer thin films were prepared using a sol–gel method and deposited on glass substrate by spin coating technique. Thin films were characterized using XRD, FE-SEM, AFM, UV–Vis spectroscopy and water contact angle measurements. XRD analysis reveals that the existence of pure anatase phase TiO₂ crystallites in the thin films. FE-SEM analysis confirms the homogeneous dispersion of TiO₂ on SiO₂ layer. Water contact angle on the thin films was measured by a contact angle analyzer under UV light irradiation. The photocatalytic performance of the TiO₂ and SiO₂/TiO₂ thin films was studied by the degradation of methylene blue under UV irradiation. The effect of an intermediate SiO₂ layer on the photocatalytic performance of TiO₂ thin films was examined. SiO₂/TiO₂ double layer thin films showed enhanced photocatalytic activity towards methylene blue dye.     

Insulating oxide buffer layer formed by sol–gel method for planarization of stainless steel substrate of a-Si:H thin film solar cell

The planarization of flexible stainless steel (SS) foils was investigated for the application of flexible solar cells. The sol–gel SiO₂ film containing nanoparticles was evaluated for a buffer layer on SS foils, and methods to improve the adhesion of SiO₂ film to SS foil were studied. The improvement of adhesion by adding Al₂O₃ matrix was discussed by analyzing the interface between Al₂O₃–SiO₂ film and SS foil. The usefulness of sol–gel buffer layer was also verified by comparing the performance of single junction a-Si:H thin film solar cells fabricated on bare SS foil and buffer layer-coated SS foil. The cell characteristics such as V_oc, J_sc, fill factor, and efficiency were all improved by adopting the buffer layer. The efficiency of the cell on buffer layer-coated and non-textured SS foil was 6.1% whereas the efficiency was 4.9% on bare SS foil.     

Photocatalytic degradation of methylene blue by Au-deposited TiO<Subscript>2</Subscript> film under UV irradiation

A TiO₂ photocatalytic film was prepared by the sol–gel and dip-coating methods. Au-loaded TiO₂ photocatalytic films were produced by the photodeposition method. The photocatalytic activity of the films under UV irradiation was evaluated by measuring the degradation of absorbance for a methylene blue (MB) aqueous solution. Au particles deposited on the TiO₂ film improved the photocatalytic activity under the O₂ bubbling condition. On the other hand, under N₂ or Ar bubbling, the doubly reduced form of MB, leuco-methylene blue (LMB), was formed at the beginning of UV irradiation, and then both MB and LMB were decomposed gradually by the photocatalytic reaction. In this process, Au particles on the TiO₂ film behave as electron traps.     

Electrochemical corrosion behaviors of titanium covered by various TiO<Subscript>2</Subscript> nanotube films in artificial saliva

TiO₂ nanotube films obtained by anodization have shown great promise as biomaterials. In the present work, we report on the corrosion behaviors of titanium (Ti) with various TiO₂ nanotubes prepared by using controlled anodization procedures. Special emphasis is put on the impact of film morphologies on the corrosion resistance of the Ti substrate. The corrosion behaviors of Ti with different nanotube films were studied in artificial saliva using open-circuit potential measurement, potentiodynamic polarization, and electrochemical impedance spectroscopy techniques. Ti covered by TiO₂ nanotube films showed the markedly enhanced corrosion resistance properties compared to bare Ti. The existence of the compact oxide layer formed in a fluoride-free electrolyte was found to be beneficial for improving corrosion resistance properties. Besides, the TiO₂ nanotube films obtained by two-step anodization had better corrosion resistance than those obtained by single-step anodization, though they used the identical anodization parameters.     

Visible light photocatalytic degradation of paraoxon and parathion pesticides on carbon-doped TiO<Subscript>2</Subscript> nanorod thin films

In the present work the nanostructured carbon-doped TiO₂ thin films with nanorod morphology were deposited on glass substrate by a combination of ultrasonic and chemical vapor deposition methods, and for the first time were applied for the photocatalytic degradation of paraoxon and parathion organophosphorus pesticides under visible light irradiation. X-ray Diffraction, X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy, and scanning electron microscopy techniques were used for characterization of the prepared thin films. Obtained results show that presence of carbon element and also special nanorod morphology of the thin films remarkably improve the optical properties of TiO₂ in visible light region and results in the good visible light photocatalytic activity of the thin films for degradation of the pesticides. The photonic efficiencies of the prepared thin films were also examined based on the international ISO-10678:2010 standard protocol for photocatalytic degradation of methylene blue under UV light irradiation. The results show a maximum photonic efficiency of 0.0312% for the carbon-doped TiO₂ thin film with 570 nm thickness, which compared to a reference standard TiO₂ films indicates a 30% improvement in photonic efficiency.     

Photoinduced properties of nanocrystalline TiO<Subscript>2</Subscript> sol-gel derived thin films

In this paper, nanostructure TiO₂ thin films were deposited on glass substrates by sol-gel dip coating technique. X-ray diffraction and Fourier transform infrared spectroscopy were used to determine film behaviour. The super-hydrophilicity was assessed by contact angle measurement. Photocatalytic properties of these films were evaluated by degradation of methylene blue under UV irradiation. The XRD pattern of TiO₂ powder samples confirmed the presence of polycrystalline anatase phase with a crystal size of 17 nm. The results indicated that UV light irradiation had significant effect on super-hydrophilic and photocatalytic properties of TiO₂ thin films.     

Preparation, characterization and photocatalytic activity of in situ Fe-doped TiO2 thin films

Fe-doped TiO₂ thin films were prepared in situ on stainless steel substrates by liquid phase deposition, followed by calcination at various temperatures. It was found that some Fe³⁺ ions were in situ doped into the TiO₂ thin films. At 400 °C, the film became photoactive due to the formation of anatase phase. At 500 °C, the film showed the highest photocatalytic activity due to an optimal Fe³⁺ ion concentration in the film. At 900 °C, the photocatalytic activity of the films decreased significantly due to the further increase of Fe³⁺ ion concentration, the formation of rutile phase and the sintering and growth of TiO₂ crystallites.     

Magnetron sputtered TiO2 films on a stainless steel substrate: Selective rutile phase formation and its tribological and anti-corrosion performance

In this work, TiO₂ films on 316L stainless steel have been formed by non-reactive magnetron sputtering of TiO₂ target. The effect of a titanium underlayer on the crystalline phase of the TiO₂ film has been investigated in terms of phase evolution, film morphology, corrosion resistance, adhesion strength, hardness and tribological characteristics. Results showed that the titanium underlayer has a significant effect on the phase of the TiO₂ film. Without this underlayer, an anatase TiO₂ film is produced, in consistence with many other investigations. However, it is found that with a titanium underlayer, a rutile TiO₂ film can be directly formed on the substrate. The thickness of the interface layer affects the crystallinity of the rutile film. By controlling the underlayer thickness, the resultant rutile film crystal structure and morphology could be changed accordingly. At an optimized state, the rutile coating shows much improved adhesion, friction, wear and corrosion properties.     

Enhanced photocatalytic activity of TiO2 by polydimethylsiloxane deposition and subsequent thermal treatment at 800 °C

A thin film of polydimethylsiloxane (PDMS) was coated on TiO₂ nanoparticles (P-25, Dagussa), and surface structures of the thin films were analyzed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Furthermore, photocatalytic activity of PDMS-coated TiO₂ samples with various annealing temperatures was determined using UV irradiation. We show that the 800 °C-annealed sample of PDMS-coated TiO₂ showed a two-fold higher photocatalytic activity with respect to the bare TiO₂. The enhanced photocatalytic activity was attributed to the greater hydrophilicity of the annealed PDMS coating.     

Construction of TiO<Subscript>2</Subscript> NP@TiO<Subscript>2</Subscript> NT double-layered structural photoanode to enhance photovoltaic performance of CdSe/CdS quantum dots sensitized solar cells

TiO₂ nanoparticles (NP) at top of TiO₂ nanotube (TiO₂ NP@TiO₂NT) double-layered architecture is constructed to combine the advantages of TiO₂ NP and TiO₂ NT together. This composite TiO₂ NP@TiO₂NT architecture as photoanode possesses a larger surface area for more QDs loading, and highly tubular structure for electron swift transport. Based on this architecture, CdSe/CdS quantum dots (QDs) have been successfully synthesized by successive ionic layer adsorption reaction (SILAR) method for quantum dots-sensitized solar cell application. The photovoltaic performance of QDSSCs based on TiO₂ NP@TiO₂ NT have been investigated in contrast with bare TiO₂ NP and bare TiO₂ NT architectures with almost the same thickness. The results show that the power conversion efficiency (PCE) of QDSSCs could be enhanced using TiO₂ NP@TiO₂ NT and improved to 3.26%, which is 80% and 38% higher than QDSSCs based on bare TiO₂ NT and bare TiO₂ NP, respectively. The BET surface area, UV–vis absorption spectra, and incident photon to current conversion efficiency (IPCE) measurements results show the evidence that the TiO₂ NP@TiO₂ NT can combine advantages of TiO₂ NP and TiO₂ NT structures together and lead to a higher light harvesting efficiency, electron collecting efficiency, and efficient electron transport.     

Titanium oxy-nitride films deposited on stainless steel by an ion beam assisted deposition technique

Surfaces of stainless steel SUS304 were coated with titanium oxy-nitride (TiON) films at temperatures of 400–770°C using an ion-beam assisted deposition technique constructed from an electron beam evaporator for Ti evaporation and a microwave ion source for ionizing nitrogen gas. The N ions were accelerated at energies of 0.5–2.0 keV. Most of the deposited TiON films consisted of (60–80)% TiN and (40–20)% TiO₂, and the fraction of TiO₂ increased with increasing substrate temperature. Hardness of the TiNO films varied in the range from 160 GPa to 260 GPa with increasing substrate temperature. The titanium oxy-nitride film could be deposited on stainless steel without a significant deterioration surface layer at 600°C. However, when TiNO films were deposited at temperatures higher than 700°C, the thickness of the TiNO films were significantly thinner and a thick layer containing nitride such as Cr₂N, CrFe, Fe₂N and Fe₄N was formed in a near surface region of stainless steel because more nitrogen diffused into stainless steel.     

Synthesis of iron-doped TiO2 nanoparticles by ball-milling process: the influence of process parameters on the structural,optical, magnetic,and photocatalytic properties

Titanium dioxide (TiO₂) absorbs only a small fraction of incoming sunlight in the visible region thus limiting its photocatalytic efficiency and concomitant photocatalytic ability. The large-scale application of TiO₂ nanoparticles has been limited due to the need of using an ultraviolet excitation source to achieve high photocatalytic activity. The inclusion of foreign chemical elements in the TiO₂ lattice can tune its band gap resulting in an absorption edge red-shifted to lower energies enhancing the photocatalytic performance in the visible region of the electromagnetic spectrum. In this research work, TiO₂ nanoparticles were doped with iron powder in a planetary ball-milling system using stainless steel balls. The correlation between milling rotation speeds with structural and morphologic characteristics, optical and magnetic properties, and photocatalytic abilities of bare and Fe-doped TiO₂ powders was studied and discussed.     

Ba<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>TiO<Subscript>3</Subscript> ferroelectric nanofilms on silicon buffered with a TiO<Subscript>2</Subscript> layer

Polycrystalline, 50- to 70-nm-thick barium strontium titanate films of composition Ba_0.8Sr_0.2TiO₃ have been grown on single-crystal silicon substrates by rf ion-beam sputtering. We have determined their structure and composition and detected impurities at the film/substrate interface in the form of titanium silicide islands. The deposition of a 4- to 6-nm-thick TiO₂ buffer layer onto Si by ion-beam sputtering before ferroelectric film growth is shown to prevent uncontrolled formation of impurities near the interface. The buffered heterostructures possess high thermal stability.     

Fabrication of thin film dye sensitized solar cells with solar to electric power conversion efficiency over 10%

Techniques of TiO₂ film fabrication for dye-sensitized solar cells having a conversion efficiency of global air mass 1.5 (AM 1.5, 1000 W/m²) solar light to electric power over 10% are reported. Newly implemented fabrication technologies consist of pre-treatment of the working photoelectrode by TiCl₄, variations in layer thickness of the transparent nanocrystalline-TiO₂ and applying a topcoat light-scattering layer as well as the adhesion of an anti-reflecting film to the electrode's surface. TiCl₄ treatments induce improvements in the adhesion and mechanical strength of the nanocrystalline TiO₂ layer. Optimization of the thickness of the TiO₂ layer, acting as the working electrode, affects both the photocurrent and the photovoltage of the devices. Covering of the TiO₂ photoanode by an anti-reflecting film results in enhancement of the photocurrent. Each of these components of film fabrication exerts a significant influence on the overall photovoltaic parameters of the devices resulting in improvements in the net energy conversion performance.     

Preparation,characterization and photocatalytic activity of TiO<Subscript>2</Subscript> / Methylcellulose nanocomposite films derived from nanopowder TiO<Subscript>2</Subscript> and modified sol–gel titania

TiO₂—methylcellulose (MC) nanocomposite films processed by the sol-gel technique were studied for phocatalytic applications. Precalcined TiO₂ nanopowder was mixed with a sol and heat treated. The sol suspension was prepared by first adding titanium tetra isopropoxide (Ti(OPr)₄ or TTP) to a mixture of ethanol and HCl (molar ratio TTP:HCl:EtOH:H₂O = 1:1.1:10:10) and then adding a 2 wt.% solution of methylcellulose (MC). The TiO₂ nanopowder was dispersed in the sol and the mixture was deposited on a microscope glass slide by spin coating. Problems of film inhomogeneity and defects which caused peeling and cracking during calcinations, because of film shrinkage, were overcome by using MC as a dispersant. Effect of MC on the structure evaluation, crystallization behavior and mechanical integrity with thermal treatment up to 500 °C are followed by SEM, XRD and scratch test. XRD Scanning electron microscopy (SEM) showed that the composite films with MC have much rougher surface than films made without MC. Composite films heat treated at approximately 500 °C have the greatest hardness values. For the composite thick film, the minimum load which caused the complete coating removal was 200 g/mm², an indication of a strong bond to the substrate. Photocatalytic activities of the composite film were evaluated through the degradation of a model pollutant, the textile dye, Light Yellow X6G (C.I. Reactive Yellow 2) and were compared with the activity of (i) a similar composite film without MC, and (ii) a TiO₂ nanopowder. The good mechanical integrity make this composite film an interesting candidate for practical catalytic applications.     

Synthesis and characterization of photosensitive TiO<Subscript>2</Subscript> nanorods by controlled precipitation route

Nanocrystalline TiO₂ thin films have been successfully synthesized by controlled precipitation route. These films are further annealed at 623 K for 2 h. The change in structural, morphological, optical, and wettability properties are studied by means of X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), scanning electron microscopy (SEM), optical absorption, and contact angle measurement. From the XRD pattern it is clear that the as-grown TiO₂ films are amorphous in nature which becomes polycrystalline after annealing. The FTIR study reveals the formation of TiO₂ compound. Scanning electron micrographs shows that the as-grown TiO₂ film consists of agglomerated nanograins well covered to the substrate surface which gets converted into vertical nanorods after annealing. As-deposited and annealed TiO₂ films showed hydrophilic behavior as water contact angles were 24° and 32°, respectively. The optical absorption study reveals the small red shift due to annealing and attributed to grain size. The annealed TiO₂ film showed conversion efficiency of 0.037% in photoelectrochemical cell with 1 M NaOH electrolyte.     

Changes in dewetting behavior of SiO<Subscript>2</Subscript> films on TiO<Subscript>2</Subscript> substrates due to film thickness and crucible choice

The TiO₂/SiO₂ materials system has had renewed interest in recent years due to its photoelectric and photocatalytic properties, and serves as an ideal model system for liquid-phase sintering studies (LPS). In this study, glass SiO₂ films of three different nanoscale thicknesses were deposited onto (001) rutile TiO₂ substrates. The resulting dewet patterns of the glass were found to change depending on the initial film thickness when subjected to identical annealing conditions. In addition, changing the crucible type from Pt to Al₂O₃, caused films of the same thickness to undergo different convection mechanisms and thus developing very different surface patterns. It is proposed that Marangoni convection drove pattern formation when a Pt crucible was used, while the Rayleigh instability was responsible for dewetting when an Al₂O₃ crucible was used.     

Characterization and photocatalytic activity of boron-doped TiO<Subscript>2</Subscript> thin films prepared by liquid phase deposition technique

Boron doped TiO₂ thin films have been successfully deposited on glass substrate and silicon wafer at 30°C from an aqueous solution of ammonium hexa-fluoro titanate and boron trifluoride by liquid phase deposition technique. The boric acid was used as an F ⁻ scavenger. The resultant films were characterized by XRD, EDAX, UV and microstructures by SEM. The result shows the deposited film to be amorphous which becomes crystalline between 400 and 500°C. The EDAX and XRD data confirm the existence of boron atom in TiO₂ matrix and a small peak corresponding to rutile phase was also found. Boron doped TiO₂ thin films can be used as photocatalyst for the photodegradation of chlorobenzene which is a great environmental hazard. It was found that chlorobenzene undergoes degradation efficiently in presence of boron doped TiO₂ thin films by exposing its aqueous solution to visible light. The photocatalytic activity increases with increase in the concentration of boron.     

Microstructure of brazed joints between mechanically metallized Si<Subscript>3</Subscript>N<Subscript>4</Subscript> and stainless steel

Brazing has been increasingly used to join metals to advanced ceramics. Brazing covalent materials requires either the use of active filler alloys or the previous metallization of the surface. To that end, a new and simple mechanical technique has been applied to metallize advanced ceramics, thus avoiding the use of costly Ti-based active filler alloys. The mechanical metallization of Si₃N₄ with Ti was employed as an alternative route to deposit active metallic films prior to brazing with stainless steel using 72% Ag--28% Cu or 82% Au—18% Ni eutectic alloys. The brazing temperatures were set to 40°C or 75°C above the eutectic temperature of each filler alloy. Ti-films of average thickness 4 μm produced adequate spreading of both filler alloys onto Si₃N₄ substrates, which were subsequently brazed to stainless steel. The interface of Si₃N₄/310 stainless steel basically consisted of a reaction layer, a precipitation zone and an eutectic microconstituent. Mechanically sound and vacuum-tight joints were obtained, especially upon brazing at relatively lower temperatures. Increasing the brazing temperature resulted in thermal cracking of the Si₃N₄, possibly due to increased thermal stress.