Structural and polarization properties of polyimide/TiO2 nanocomposites

Polyimide (PI)/titanium dioxide (TiO₂) nanocomposite films were prepared by a solution mixing method with different contents of TiO₂ nanoparticles. The structural and thermal properties of pure PI and PI/TiO₂ nanocomposite films were studied by several techniques such as scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and thermally stimulated depolarization current (TSDC). The SEM and AFM measurements show the uniform dispersion of TiO₂ nanoparticles in PI matrix, and it is also observed that the value of average roughness increases with increasing the contents of TiO₂ nanoparticles. The XRD pattern shows the presence of TiO₂ nanoparticles in PI matrix. It has been observed that the average crystallite size and percentage of crystallinity increase with content of the TiO₂ nanoparticles. FTIR spectra depict the position of different bonds in PI and nanocomposite samples. The TSDC results represent the modification of polarization phenomenon after filling of PI by titania nanoparticles.     

Photocatalytic properties of TiO2 thin films obtained by glancing angle deposition

Titanium dioxide (TiO₂) thin films with different nanostructures such as nano-particles and separated vertical columns were grown by glancing angle deposition (GLAD) in an electron beam evaporation system. The photocatalytic properties of grown TiO₂ films with different deposition angles and different annealing temperatures were evaluated by following decomposition of methyl orange under ultraviolet (UV) light irradiation. The results suggest that increased surface area due to the GLAD process could improve the photocatalytic properties of TiO₂ films.     

Raman evidence of the interaction between multiwalled carbon nanotubes and nanostructured TiO2

Nanocomposites of carbon nanotubes and titanium dioxide (TiO₂) have attracted much attention due to their photocatalytic properties. Although many examples in the literature have visualized these nanocomposites by electron microscopic images, spectroscopic characterization is still lacking with regard to the interaction between the carbon nanotube and TiO₂. In this work, we show evidence of the attachment of nanostructured TiO₂ to multiwalled carbon nanotubes (MWNTs) by Raman spectroscopy. The nanostructured TiO₂ was characterized by both full‐width at half‐maximum (FWHM) and the Raman shift of the TiO₂ band at ca 144 cm⁻¹, whereas the average diameter of the crystallite was estimated as approximately 7 nm. Comparison of the Raman spectra of the MWNTs and MWNTs/TiO₂ shows a clear inversion of the relative intensities of the G and D bands, suggesting a substantial chemical modification of the outermost tubes due to the attachment of nanostructured TiO₂. To complement the nanocomposite characterization, scanning electronic microscopy and X‐ray diffraction were performed. Copyright © 2011 John Wiley & Sons, Ltd.     

Enhanced photocatalytic degradation of Safranin-O by heterogeneous nanoparticles for environmental applications

Nanostructure titanium dioxide (TiO₂) has been synthesized by hydrolysis of titanium tetrachloride in aqueous solution and Ag-TiO₂ nanoparticles were synthesized by photoreduction method. The resulting materials were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier-transform infrared (FT-IR) and UV-vis absorption spectroscopy. The experimental results showed that the sizes of the synthesized TiO₂ and Ag-TiO₂ particles are in the range of 1.9-3.2 nm and 2-10 nm, respectively. Moreover, Ag-TiO₂ nanoparticles exhibit enhanced photocatalytic activity on photodegradation of Safranin-O (SO) dye as compared to pure TiO₂. The positive effect of silver on the photocatalytic activity of TiO₂ may be explained by its ability to trap electrons. This process reduces the recombination of light generated electron-hole pairs at TiO₂ surface and therefore enhances the photocatalytic activity of the synthesized TiO₂ nanoparticles. The effects of initial dye and nanoparticle concentrations on the photocatalytic activity have been studied and the results demonstrate that the dye photodegradation follows pseudo-first-order kinetics. The observed maximum degradation efficiency of SO is about 60% for TiO₂ and 96% for Ag-TiO₂.     

Synthesis and characterization of TiO2 thin films coated on metal substrate

Nanostructured titanium dioxide (TiO₂) thin films have been prepared on metal substrates using a facile layer-by-layer dip-coating method. The phase structure and morphologies of preparing samples were characterized by means of X-ray powder diffraction (XRD) and field-emission scanning electron microscopy (FESEM). The results confirm that films are highly crystalline anatase TiO₂ and free from other phases of titanium dioxide. Scanning electron microscopy (SEM) shows that the nanoparticles are sintered together to form a compact structure. The electrical properties of samples were investigated by cutternt-voltage analysis, the result indicates that a rectifying junction between the nanocrystalline TiO₂ film and metal substrate was formed. The photoelectrochemical characteristics recorded under 1.5 AM illumination indicates that the as-fabricated thin film electrode possesses the highest photocurrent density at 450 °C, which is 1.75 mA/cm² at 0 V vs. Ag/AgCl.     

Composite SiO2/TiO2 and amine polymer/TiO2 nanoparticles produced using plasma-enhanced chemical vapor deposition

Plasma-enhanced chemical vapor deposition was used to conformally coat commercial TiO₂ nanoparticles to create nanocomposite materials. Hexamethyldisiloxane (HMDSO)/O₂ plasmas were used to deposit SiO₂ or SiO_xC_yH_z films, depending on the oxidant concentration; and hexylamine (HexAm) plasmas were used to deposit amorphous amine-containing polymeric films on the TiO₂ nanoparticles. The composite materials were analyzed using Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). These analyses reveal film composition on the nanoparticles was virtually identical to that deposited on flat substrates and that the films deposit a conformal coating on the nanoparticles. The performance of the nanocomposite materials was evaluated using UV-vis spectroscopy to determine the dispersion characteristics of both SiO_x and HexAm coated TiO₂ materials. Notably, the coated materials stay suspended longer in distilled water than the uncoated materials for all deposited films.     

Fabrication of hydrophobic surface of titanium dioxide films by successive ionic layer adsorption and reaction (SILAR) method

Titanium dioxide (TiO₂) films were fabricated on fluorine doped tin oxide (FTO) coated glass substrate using successive ionic layer adsorption and reaction (SILAR) method. The X-ray diffraction, scanning electron microscopy, transmission electron microscopy, optical absorption and contact angle measurement were applied to study the structural, surface morphological, optical and surface wettability properties of the as-deposited and annealed TiO₂ films. The X-ray diffraction studies revealed both as-deposited and annealed TiO₂ films are amorphous. Irregular shaped spherical grains of random size and well covered to the fluorine doped tin oxide coated glass substrates were observed from SEM studies with some cracks after annealing. The optical band gap values of virgin TiO_2, annealed, methyl violet and rose bengal sensitized TiO₂ were found to be 3.6, 3.5, 2.87 and 2.95 eV, respectively. Surface wettability studied in contact with liquid interface, showed hydrophobic nature as water contact angles were greater than 90°. The adsorption of dyes, as confirmed by the photographs, is one of the prime requirements for dye sensitized solar cells (DSSC).     

Preparation and performance of photocatalytic TiO2 immobilized on palladium-doped carbon fibers

Pd-modified carbon fibers (CFs) are obtained by a facile oxidation-reduction method and then dip-coated in a sol-gel of titanium dioxide (TiO₂) to form supported TiO₂/Pd-CF photocatalysts. The morphology of the Pd-modified CFs and the amount Pd deposited are characterized by field emission scanning electron microscopy and atomic absorption spectrometry, respectively. X-ray diffraction is used to investigate the crystal structures of the TiO₂ photocatalyst. Acid orange II is used as a model contaminant to evaluate the photocatalytic properties of the photocatalyst under UV irradiation. TiO₂/Pd-CF exhibits higher catalytic activity than TiO₂/CF towards the degradation of acid orange II. Optimum photocatalytic performance and support properties are achieved when the Pd particle loading is about 10.8 mg/g.     

Improvement in thermo mechanical and optical properties of in situ synthesized PMMA/TiO2 nanocomposite

In this paper, transparent thin films of nano titania filled Poly(methyl methacrylate) (PMMA) composites were synthesized by solvent casting method using tetra hydro furan as a solvent, with in situ nonaqueous ‘sol-gel’ transformation involving the mixing of titanium isopropoxide (as sol-gel precursor) and methanol. The present research work is focused at studying the effect of titania loading on optical and mechanical behavior of transparent nano hybrid thin films. The effect of nano Titanium dioxide (TiO₂) loading on PMMA morphology was studied by using a scanning electron microscope (SEM). Bowl shaped structures were obtained in pure PMMA thin film, which were deformed on incorporation of TiO₂ nanoparticles. This nanocomposite exhibits enhanced optical and mechanical properties. The peak of UV absorption is blue shifted to 261 and 266?nm with the incorporation of TiO₂. At this wavelength, the absorption is increased up to approximately 397%. The nanocomposites exhibit increased tensile strength up to 40% and modulus up to 16%. Tg of PMMA increased from 84.8 to 86.7?°C on adding 1.25% TiO₂ nanoparticles.     

Electron transport in dye-sensitized solar cells based on TiO2 nanowires

Anatase titanium dioxide nanowire arrays were prepared by hydrothermally oxidizing titanium foils in aqueous alkali and transferred onto fluorinated tin oxide(FTO)glass for use as the photoanodes of front side illuminated dye-sensitized solar cells(DSCs).Electrochemical impedance spectroscopy(EIS)measurement was applied to compare the electron transport and recombination properties of DSCs using TiO2nanowire films and TiO2nanoparticle films as photoanodes.It was found that the nanowire array films possess smaller electron transport resistance(Rt)and larger electron diffusion length(Le)in the photoanodes,suggesting that the nanowire arrays can enhance the electron transport rate and have a potential to improve the charge collection efficiency of DSCs.     

Cobalt-doped TiO2: a computational analysis of dopant placement and charge transfer direction on thin film anatase

ABSTRACT

Titanium dioxide (TiO₂) nanocrystals are promising materials for photo-electrochemical water splitting. This study focuses on how surface dopant placement can affect the electronic properties. TiO₂ anatase thin films are doped two ways: a cobalt ion replacing a surface titanium ion (surface ingrained) and a cobalt ion chemisorbed to two surface oxygen ions and two NH₃ ligands. Specifically, when studying the binding pattern, the cobalt ion dopant changes from an electron acceptor for the surface ingrained model to an electron donor for the chemisorbed model. The optical absorption peaks of the surface ingrained model are attributed to p→d transitions and are much stronger when compared to the d→d transitions for the chemisorbed model. It is the conclusion of this computational study that one can alter the cobalt dopant on the anatase thin film to focus a positive or negative charge at the surface by changing the surface dopant location.     

Phonon confinement in individual titanium dioxide nanowires

Size effects on the phonon modes have been unambiguously observed on single individual titanium dioxide (TiO₂) nanowire using Raman spectroscopy. A template-free oxidation process using ethanol vapor was developed to control the growth and the density, length, and size distribution of the TiO₂ nanowires. Scanning electron microscopy, transmission electron microscopy, and X-ray diffraction were used to characterize the morphology, crystalline phases and microstructures. Using a confocal laser probe, Raman spectroscopy revealed in the individual rutile TiO₂ nanowire, the E_g, A_1g vibration modes which are confined in the radial directions. Along the single-crystalline nanowire axis, the systematic size-dependent variations in the center-shift, broadening as well as the shape asymmetry of the Raman peaks can be well explained in terms of the phonon confinement model.     

Synthesis and characterisations of Au-nanoparticle-doped TiO2 and CdO thin films

In the present study, pure and gold nanoparticle (Au NP)-doped titanium dioxide (TiO₂) and cadmium oxide (CdO) thin film were prepared by the sol–gel method, and the effect of Au NP doping on the optical, structural and morphological properties of these thin films was investigated. The prepared thin films were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM) and ultraviolet–visible–near infrared (UV–Vis–NIR) spectra. While the optical band increases from 3.62 to 3.73 for TiO₂ thin films, it decreases from 2.20 to 1.55 for CdO thin films with increasing Au doping concentration. Analysis of XRD indicates that the intensities of peaks of the crystalline phase have increased with the increasing Au NP concentrations in all thin films. SEM images demonstrate that the surface morphologies of the samples were affected by the incorporation of Au NPs. Consequently, the most significant results of the present study are that the Au NPs can be used to modify the optical, structural and morphological properties of TiO₂ and CdO thin films.     

Nanoparticulate cerium dioxide and cerium dioxide-titanium dioxide composite thin films on glass by aerosol assisted chemical vapour deposition

Two series of composite thin films were deposited on glass by aerosol assisted chemical vapour deposition (AACVD)—nanoparticulate cerium dioxide and nanoparticulate cerium dioxide embedded in a titanium dioxide matrix. The films were analysed by a range of techniques including UV-visible absorption spectroscopy, X-ray diffraction, scanning electron microscopy and energy dispersive analysis by X-rays. The AACVD prepared films showed the functional properties of photocatalysis and super-hydrophilicity. The CeO₂ nanoparticle thin films displaying photocatalysis and photo-induced hydrophilicity almost comparable to that of anatase titania.     

Oxygen stoichiometry controlled sharp insulator-metal transition in highly oriented VO2/TiO2 thin films

The insulator-metal transition (IMT) in vanadium dioxide (VO₂) which occurs above room temperature (67 °C) is highly sensitive to atomic defects caused by oxygen stoichiometry. The strained growth and the degree of oxygen deficiency in VO₂ epitaxial films result in lowering of transition temperature below room temperature as well as the broadening of transition parameters such as transition width and hysteresis width, which limit its application potential. Here we demonstrate the growth of highly oriented strain-relaxed VO₂ thin films on (001)-oriented TiO₂ substrates at various oxygen partial pressures, exhibiting the narrow transition and hysteresis width. The cross-sectional transmission electron microscopy and x-ray diffraction analyses of the films reveal the highly oriented growth of insulating monoclinic VO₂. The IMT parameters associated with temperature-dependent phase transition vary with the oxygen partial pressure used during the deposition. The presence of multiple and mixed valence states of vanadium in the films was confirmed by Raman and XPS analyses. We have achieved a narrow transition width (2.3 °C) and hysteresis width (1.2 °C) through controlling the oxygen stoichiometry during the growth of VO₂/TiO₂ films.     

Use of successive ionic layer adsorption and reaction (SILAR) method for amorphous titanium dioxide thin films growth

Use of successive ionic layer adsorption and reaction (SILAR) method was preferred for the growth of amorphous titanium dioxide (TiO₂) thin films at ambient temperature. Further, these films were annealed at 673 K for 2 h in air for structural improvement and characterized for structural, surface morphological, optical and electrical properties. An amorphous structure of TiO₂ was retained even after annealing as confirmed from XRD studies. The spherical grains of relatively large size were compressed after annealing. A red shift in band gap energy and decrease in electrical resistivity were observed due to annealing treatment.     

Electrophoreted Zn-TiO2-ZnO nanocomposite coating films for photocatalytic degradation of 2-chlorophenol

TiO₂-ZnO nano-powders with different TiO₂/ZnO ratios have been synthesized by hydrothermal method. Nanocomposite coating films consisting of TiO₂-ZnO and Zn with thickness of 20 μm have been electrophoreted on steel plates by rapid plating from a ZnO-based alkaline bath. X-ray diffraction, scanning electron microscopy and energy dispersive X-ray analysis were used to investigate the structure, the size distribution, and the composition of prepared nano-powders and plated materials. The effect of the operating parameters such as powder contents, pH and current density on the electrophoresis process has been investigated and optimum conditions of coating process were determined. Corrosion properties of plated samples have been studied by salt spray test. The catalytic activity of the prepared nanocomposite Zn-TiO₂-ZnO films for the photocatalytic degradation of 2-chlorophenol (2-CP) was measured.     

Reactive sputtering TiO2 films for surface coating of poly(dimethylsiloxane)

Titanium dioxide (TiO₂) films were prepared on poly(dimethylsiloxane) (PDMS) substrate by direct current (DC) reactive sputtering to change surface physical properties of PDMS. The effects of the changes were investigated by using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) analysis, water contact angle measurements and protein adsorption tests. Improved wettability and reduced adsorption properties were observed on PDMS surface coated TiO₂ films.     

Oriented single crystalline TiO2 nano-pillar arrays directly grown on titanium substrate in tetramethylammonium hydroxide solution

Oriented single crystalline titanium dioxide (TiO₂) nano-pillar arrays were directly synthesized on the Ti plate in tetramethylammonium hydroxide (TMAOH) solution by one-pot hydrothermal method. The samples were characterized respectively by means of field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and X-ray diffraction (XRD). Results showed that the TiO₂ nano-pillar with a tetrahydral bipyramidal tip grew vertically on the titanium substrate. HRTEM and Raman results confirmed that the TiO₂ nano-pillar arrays were single crystalline anatase. The controls of morphology, size, and orientation of the nano-pillar could be achieved by varying the solution concentration and hydrothermal temperature. Furthermore, the special morphology of the TiO₂ nano-pillar arrays was caused by the selectively absorption of the tetramethylammonium (TMA) through hydrogen bonds on the lattice planes parallel to (0 0 1) of anatase TiO₂. Less grain boundaries and direct electrical pathway for electron transferring were crucial for the superior photoelectrochemical properties of the single anatase TiO₂ nano-pillar arrays. This approach provides a facile in situ method to synthesize TiO₂ nano-pillar arrays with a special morphology on titanium substrate.     

Super-hydrophilic properties of TiO2-DLC nanocomposite films fabricated by the simple electrochemical process

Anatase TiO₂ nanoparticles incorporated DLC films were successfully deposited on single crystalline silicon substrates by the electrolysis of TiO₂-methanol solution under ambient atmospheric pressure and low temperature. Anatase TiO₂ nanoparticles were embedded into amorphous carbon matrix, forming the typical nanocrystalline/amorphous nanocomposite films, confirmed by transmission electron microscopy (TEM). TiO₂ incorporation effectively increased the sp³-hybridized carbon concentration in the composite film, and further regulated the microstructure and surface morphology. Furthermore, the static contact testing completely displayed, TiO₂ incorporation got the composite films super-hydrophilic, which fundamentally improved the wetting ability of DLC film.