Nanostructured leaf like hydroxyapatite/TiO2 composite coatings by simple sol-gel method

We demonstrate an approach for the coating of nanostructured leaf like hydroxyapatite (HAp)/TiO₂ composite on glass substrate by sol-gel dip coating process. HAp/TiO₂ nanocomposite thin film was obtained by controlling the dipping rate and the dipping cycle. It was observed from Scanning Electron Microscope that leaf like nanostructured film was deposited on the glass substrate. However, the structure of the film was changed with the dipping cycle and dipping rate. Transmission Electron Microscopic analysis further confirms the morphology of the nanostructured coatings. The presence of Ti, O, Ca and P was detected by Energy Dispersive X-ray Analysis. We further confirmed the composite by X-ray diffraction analysis. Atomic Force Microscope analysis indicates that the films are composed of nanoparticles ranging from 100 to 200 nm and the films were observed to present well-defined grain boundaries. It has been shown that nanocomposite coatings are dependent on the sol concentration, dipping parameters, and the composition of HAp and TiO₂.     

Mechanical and photocatalytic properties of hydroxyapatite/titania nanocomposites prepared by combined high gravity and hydrothermal process

Hydroxyapatite/titania nanocomposites of different ratios have been successfully synthesized by combined high gravity and hydrothermal methods. SEM and TEM observations showed that small spheres of TiO₂, identified as anatase crystals of 10–15 nm, were deposited on HAp rod-like crystals. EDAX analysis confirmed the presence of Ca, P, Ti and O. X-ray diffraction patterns indicated the presence of hydroxyapatite and anatase phase. More number of anatase peaks appeared in the XRD patterns with higher colloidal concentration of TiO₂ in the HAp/TiO₂ compound. Mechanical stability of the HAp/TiO₂ nanocomposites was determined by reinforcing them with high molecular weight polyethylene (HMWPE) and the tensile strength of the samples was analyzed. Photocatalytic activity of the HAp/TiO₂ particles was examined by decomposition of methyl orange (MO). The results showed that photocatalytic properties of HAp/TiO₂ composites are more effective than that of individual HAp and TiO₂ which implied that the HAp improved the photocatalytic activity of well known photocatalyst TiO₂.     

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).     

Fluoridated hydroxyapatite/titanium dioxide nanocomposite coating fabricated by a modified electrochemical deposition

Fluoridated hydroxyapatite/titanium dioxide nanocomposite coating was successfully fabricated by a modified electrochemical deposition technique. F⁻ ions, nanoscaled TiO₂ particles and 6% H₂O₂ was added into the electrolyte, and ultrasonication was also performed to prepare this nanocomposite coating. The microstructure, phase composition, dissolution rate, bonding strength and in vitro cellular responses of the composite coating were investigated. The results show that the composite coating was uniform and dense owing to the effects of H₂O₂ and ultrasonication. The thickness of the composite coating was ~5 μm and scanning electron microscopy revealed that nanoscaled TiO₂ particles were imbedded uniformly between FHA crystals. The addition of F⁻ and TiO₂ reduced the crystallite size and increased the crystallinity of HA in FHA/TiO₂ composite coating. In addition, the composite coating shows higher bonding strength and lower dissolution rate than pure HA coating, and the in vitro bioactivity of FHA/TiO₂ composite coating was not affected as compared with pure HA coating.     

Rapid synthesis, characterization and optical properties of TiO2 coated ZnO nanocomposite particles by a novel microwave irradiation method

A novel and rapid microwave method was used to prepare TiO₂ coated ZnO nanocomposite particles. The resulted particles were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS). Results show that ZnO nanoparticles were coated with 6-10 nm amorphous TiO₂ layers. In addition, zeta potential analysis demonstrated the presence of TiO₂ layer on the surface of ZnO nanoparticles. Photoluminescence (PL) spectroscopy and UV-visible spectroscopy were used to investigate the optical properties of the nanoparticles. Compared to uncoated ZnO nanoparticles, the TiO₂ coated ZnO nanoparticles showed enhanced UV emission. The UV-visible diffuse reflectance study revealed the significant UV shielding characteristics of the nanocomposite particles. Moreover, amorphous TiO₂ coating effectively reduced the photocatalytic activity of ZnO nanoparticles as evidenced by the photodegradation of Orange G with uncoated and TiO₂ coated ZnO nanoparticles under UV radiation.     

Effect of temperature on the growth of TiO2 thin films synthesized by spray pyrolysis: Structural, compositional and optical properties

Large surface area coatings of oxygen deficient nanocrystalline TiO₂ are of immense use in antifogging mirrors and self cleaning windows. Spray pyrolysis is a simple versatile technique to coat relatively large surface area. A clear understanding of effect of substrate temperature on the coating morphology, structure, composition and optical properties is essential to produce coatings of desired properties. Oxygen deficient nanocrystalline anatase–TiO₂ thin films were synthesized on Si(1 0 0), quartz and glass substrates at 300–550 °C. Well defined platelets like nanograins standing on their edge were obtained at 500 °C. The crystallites were found to be of ∼12 nm thickness and ∼30 nm major diameter. The secondary ion mass spectrometric studies of the films revealed uniform distribution of titanium and oxygen across the thickness of the film up to the film–substrate interface. Presence of lower valent Ti ions and oxygen vacancies were confirmed from XPS studies. The indirect and direct band gap values evaluated from the Tauc plot for films synthesized at 500 °C are 3.3 and 3.62 eV respectively.     

Surface characterization of poly(methylmethacrylate) based nanocomposite thin films containing Al2O3 and TiO2 nanoparticles

Poly(methylmethacrylate) (PMMA) based nanocomposite electron beam resists have been demonstrated by spin coating techniques. When TiO₂ and Al₂O₃ nanoparticles were directly dispersed into the PMMA polymer matrix, the resulting nanocomposites produced poor quality films with surface roughnesses of 322 and 402 nm respectively. To improve the surface of the resists, the oxide nanoparticles were encapsulated in toluene and methanol. Using the zeta potential parameter, it was found that the stabilities of the toluene/oxide nanoparticle suspensions were 7.7 mV and 19.4 mV respectively, meaning that the suspension was not stable. However, when the TiO₂ and Al₂O₃ nanoparticles were encapsulated in methanol the zeta potential parameter was 31.9 mV and 39.2 mV respectively. Therefore, the nanoparticle suspension was stable. This method improved the surface roughness of PMMA based nanocomposite thin films by a factor of 6.6 and 6.4, when TiO₂ and Al₂O₃ were suspended in methanol before being dispersed into the PMMA polymer.     

Preparation and characterization of nanocrystalline porous TiO2/WO3 composite thin films

TiO₂ materials possessing not only photocatalytic but also electrochromic properties have attracted many research and development interests. Though WO₃ exhibits excellent electrochromic properties, the much higher cost and water-sensitivity of WO₃ as compared with the TiO₂ may restrict the practical application of WO₃ materials. In the present study, the feasibility of preparing nanocrystalline porous TiO₂/WO₃ composite thin films was investigated.Precursors of sols TiO₂ and/or WO₃ and polystyrene microspheres were used to prepare nanocrystalline pure TiO₂, WO₃, and composite TiO₂/WO₃ thin films by spin coating. The spin-coated thin films were amorphous and, after heat treating at a temperature of 500 °C, nanocrystalline TiO₂, TiO₂/WO₃, and WO₃ thin films with or without pores were prepared successfully. The heat-treated thin films were colorless and coloration-bleaching phenomena can be observed during cyclic voltammetry tests. The heat-treated thin films exhibited good reversible electrochromic behavior while the porous TiO₂/WO₃ composite film exhibited improved electrochromic properties.     

Preparation and super-hydrophilic properties of TiO2/SnO2 composite thin films

SnO₂-TiO₂ composite thin films were fabricated on soda-lime glass with sol-gel technology. By measuring the contact angle of the film surface and the degradation of methyl orange, we studied the influence of SnO₂ doping concentration, heat-treatment temperature and film thickness on the super-hydrophilicity and photocatalytic activity of the composite films. The results indicate that the doping of SnO₂ into TiO₂ can improve their hydrophilicity and photocatalytic activity, and the composite film with 1-5 mol% SnO₂ and heat-treated at 450°C is of super-hydrophilicity. The optimal SnO₂ concentration for the photocatalytic activity is 10 mol% and larger film thickness is helpful to reduce the contact angle of the composite films.     

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.     

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.     

The effect of argon pressure on the structural and photocatalytic characteristics of TiO2 thin films deposited by d.c. magnetron sputtering

TiO₂ thin films of 200-300 nm thickness were deposited by d.c. magnetron sputtering onto glass substrates from a semiconducting TiO_2−x target in pure Ar using pressures between 0.1 and 1.0 Pa. The obtained TiO₂ coatings are transparent and have refractive indices between 2.5 and 1.9. Post deposition heat treatment at different temperatures was performed to achieve crystallization of anatase TiO₂. The as-deposited and heat treated films were examined with UV-VIS (transmission), SEM and XRD to investigate the influence of the argon pressure during deposition on the structural development during heat treatment. Additionally, the photocatalytic activity of the films was tested by measuring the decomposition rate of ethanol in a controlled gas atmosphere simulating air, and was related to their respective microstructures.     

Influence of Nd dopant amount on microstructure and photoluminescence of TiO2:Nd thin films

TiO₂ and TiO₂:Nd thin films were deposited using reactive magnetron sputtering process from mosaic Ti–Nd targets with various Nd concentration. The thin films were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM) and spectroscopic techniques. Photoluminescence (PL) in the near infrared obtained upon 514.5 nm excitation was also examined. The relationship between the Nd concentration, structural, optical and photoluminescence properties of prepared thin films was investigated and discussed. XRD and TEM measurements showed that an increase in the Nd concentration in the thin films hinders the crystal growth in the deposited coatings. Depending on the Nd amount in the thin films, TiO₂ with the rutile, mixed rutile–amorphous or amorphous phase was obtained. Transmittance measurements revealed that addition of Nd dopant to titania matrix did not deteriorate optical transparency of the coatings, however it influenced on the position of the fundamental absorption edge and therefore on the width of optical band gap energy. All TiO₂:Nd thin films exhibited PL emission that occurred at ca. 0.91, 1.09 and 1.38 μm. Finally, results obtained for deposited coatings showed that titania with the rutile structure and 1.0 at.% of Nd was the most efficient in VIS to NIR photon conversion.     

Dependence of thickness on the withdrawal speed for SiO2 and TiO2 coatings obtained by the dipping method

SiO₂ and TiO₂ sol-gel thin films were prepared from solutions of different concentration. To fit the experimental coating thickness values, the modification of two theoretical equations, available from the literature, was used. The best-fit results were given by the approach which relates the thickness to the square root of the velocity. It was shown that, provided the same heat treatment is used for the films, the thickness of coatings obtained from solutions of different concentration and at any withdrawal speed may be predicted from just one thickness value obtained at one withdrawal speed, if the solutions' viscosity and density, are known.     

Hydroxyapatite-anatase-carbon nanotube nanocomposite coatings fabricated by electrophoretic codeposition for biomedical applications

In order to eliminate micro-cracks in the monolithic hydroxyapatite (HA) and composite hydroxyapatite/carbon nanotube (HA/CNT) coatings, novel HA/TiO₂/CNT nanocomposite coatings on Ti6Al4V were attempted to fabricate by a single-step electrophoretic codeposition process for biomedical applications. The electrophoretically deposited layers with difference contents of HA, TiO₂ (anatase) and CNT nanoparticles were sintered at 800°C for densification with thickness of about 7–10 μm. A dense and crack-free coating was achieved with constituents of 85 wt% HA, 10 wt% TiO₂ and 5 wt% CNT. Open-circuit potential measurements and cyclic potentiodynamic polarization tests were used to investigate the electrochemical corrosion behavior of the coatings in vitro conditions (Hanks’ solution at 37°C). The HA/TiO₂/CNT coatings possess higher corrosion resistance than that of the Ti6Al4V substrate as reflected by nobler open circuit potential and lower corrosion current density. In addition, the surface hardness and adhesion strength of the HA/TiO₂/CNT coatings are higher than that of the monolithic HA and HA/CNT coatings without compromising their apatite forming ability. The enhanced properties were attributed to the nanostructure of the coatings with the appropriate TiO₂ and CNT contents for eliminating micro-cracks and micro-pores.     

Study of Nd-doping effect and mechanical cracking on photoreactivity of TiO2 thin films

Pure and Nd-doped TiO₂ thin films were fabricated by reactive d.c. magnetron sputtering at low-temperature from a pure Ti target. The structure of films was analyzed by X-ray diffraction (XRD). In order to study the Nd-doping effect on TiO₂ photocatalytic activity, some films were deposited on microscope glass substrates under a constant total sputtering pressure and using different Nd-doping concentrations. The effect of different Nd-dopant concentrations and its influence on the photocatalytic efficiency has been explored by measuring the photodegradation of rhodamine-B (RhB) aqueous solution under radiation of UV light. It is principally that for comparison between heat treatment and doping process on TiO₂ photocatalytic efficiency (important under the point of view of energy costs related with industrial sputtering techniques), crystalline TiO₂ films were also produced by thermal annealing. It was found that comparing with annealed pure TiO₂ films, Nd-doping do not improve the photocatalytic activity. At the same time, it was observed that there seems to exist a dopant concentration band for optimal photoreactivity. In order to study the effect of the film mechanical strength on photocatalytic activity, fragmentation tensile tests were also done on TiO₂/PET (polyethylene terephthalate) substrates at increasing applied strains. It was found that increasing the magnitude of the applied tensile strain, pure TiO₂ becomes more photocatalytic efficient.     

Wear characteristics of mechanically milled TiO2 nanoparticles incorporated in electroless Ni–P coatings

Nanosized TiO₂ particles have been prepared by top down approach using mechanical milling with high energy planetary ball mill at 250 rpm for different extents of time (5, 10, 20, 30 and 40 h). Electroless (EL) Ni–P–TiO₂ nanocomposite coatings were developed using alkaline bath containing milled TiO₂ nanoparticles (4 g/l). The results show that, the morphology of TiO₂ particles milled for 40 h exhibit irregular shape with a particle diameter in the range of 33–45 nm. Wear studies of the coatings with 30 μm thickness were investigated using 1, 1.5 and 2 N loads with 0.1 and 0.2 m/s rotation speeds. The Ni–P–TiO₂ nanocomposite coatings exhibit the enhanced hardness and wear resistance as compared to that of Ni–P alloy coatings. Also the composite after heat treatment at 400 °C for 1 h in argon atmosphere showed improved hardness (1010 VHN) and wear resistance (1.5e-06 mm³/N m).     

Morphological characterization and analytical application of poly(3,4-ethylenedioxythiophene)-Prussian blue composite films electrodeposited in situ on platinum electrode chips

Electrochemical in situ preparation and morphological characterization of inorganic redox material-organic conducting polymer coatings as thin films on platinum electrodes are presented. Composite inorganic-organic coatings consist of Prussian blue (PB) and [poly(3,4-ethylenedioxythiophene)] (PEDOT), and PEDOT organic polymers doped with ferricyanide (PEDOT-FeCN). The PEDOT coating deposited from an aqueous solution containing the 3,4-ethylenedioxythiophene monomer and LiClO₄ as supporting electrolyte was used as a “reference” material (PEDOT-ClO₄). The composite coatings were prepared by electrochemical methods on platinum electrode chips, which consist of a 150 nm Pt layer deposited on 100-oriented standard 3″ silicon wafers. Electrochemical behavior of the composite inorganic-organic coatings is based mainly on inorganic component redox reactions. Different surface properties of the composite materials were studied. Thus, the roughness of the deposited films was measured by both atomic force microscopy (AFM) and profilometry, leading to roughness values ranging from 3 nm to 217 nm for PEDOT-ClO₄, and PEDOT-FeCN and PEDOT-PB coatings, respectively. AFM and Scanning Electron Microscopy pictures were also produced to characterize the film morphologies, and revealed a granular pattern of the deposited inorganic component inside the organic polymer matrix. Moreover, the adhesion properties of the composites were studied by AFM and proved to be very different from one material to the other depending on the film structure. The electrochemical responses of these composite coatings to H₂O₂ reduction were also investigated using chronoamperometry. A linear response over a concentration range from 1 × 10^− 4 to 1 × 10^− 5 M and a detection limit of 10 μM were obtained.     

Thermochromic nanocrystalline Au-VO2 composite thin films prepared by radiofrequency inverted cylindrical magnetron sputtering

Highly crystalline Au-VO₂ nanocomposite thin films were prepared on Corning glass substrates by reactive radiofrequency inverted cylindrical magnetron sputtering (ICMS). It is a low cost potential coating technology for the production of large area uniform nanocomposite thin films exhibiting plasmonic properties. This paper reports the synthesis and feasibility of reliably reproduced high quality of Au-VO₂ by ICMS. Structural, morphological, interfacial analysis and optical properties of synthesized Au-VO₂ nanocomposite thin films are reported.     

Scalable production of ultra small TiO2 nano crystal/activated carbon composites by atomic layer deposition for efficient removal of organic pollutants

A high surface area photo-catalytic composite material is synthesized by depositing thin films of titanium dioxide (TiO₂) on activated carbon (AC) particles using atomic layer deposition (ALD). A rotary ALD reactor is developed for scalable fabrication of powder and grams of the catalyst is prepared in each batch. The processes of TiO₂ ALD are monitored by mass spectrometry. Saturated ALD surface reactions are confirmed so that the entire surface of the AC support is covered by conformal coatings of TiO₂. For composites fabricated by 3 or more ALD cycles of TiO₂, the amorphous oxide layers can be converted to crystalline films by high temperature annealing. The as-prepared TiO₂/AC composites are highly reactive in photo-catalyzed degradation of methyl orange. The excellent catalytic performance is attributed to the abundant and uniformly dispersed active phase, formation of very active ultra small (<5 nm) TiO₂ crystals, and easy accessibility of the active sites.