Polyimide/nano-TiO2 hybrid films having benzoxazole pendent groups: In situ sol–gel preparation and evaluation of properties

Polyimide/titania (PI/TiO₂) nanocomposite films have been successfully fabricated through the in situ formation of TiO₂ within a PI matrix via sol–gel method. Poly(amic acid) (PAA), which is the precursor of PI, was successfully synthesized by mixing pyromellitic dianhydride (PMDA), with equimolar amount of a diamine monomer having a pendent benzoxazole unit and two flexible ether linkages in N,N-dimethylformamide (DMF) solvent. Tetraethyl orthotitanate [Ti(OEt)₄] and acetylacetone were then added to the resulted PAA. After imidization at high temperature, PI/TiO₂ hybrid films were formed. The structure and morphology of the hybrid nanocomposites with different titania contents (0 wt%, 5 wt%, 10 wt%, and 15 wt%) were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and transmission electron microscopy. The results indicate that the TiO₂ nanoparticles were homogeneously dispersed in the hybrid films. The thermogravimetric analysis of nanocomposites confirms the improvement in the thermal stability with the increase in the percentage of titania nanoparticle. Transmission electron microscopy showed that the nanoparticles with an average diameter of 25–40 nm were dispersed in the polymer matrix.     

Chitosan/TiO2 nanocomposite pervaporation membranes for ethanol dehydration

Novel chitosan/titanium dioxide (CS/TiO₂) nanocomposite membranes were prepared using tetrabutyl titanate (TBT) as precursor and acetyl acetone as chelating agent by in situ sol-gel process, and characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetry (TG). The characterization results demonstrated that nano-sized TiO₂ particles dispersed homogeneously within the CS matrix, which could be assigned to the hydrogen and titanoxane bonds formed between CS and TiO₂. Moreover, the pervaporation performance of these membranes was investigated using the separation of ethanol-water mixture as model system. Compared with CS/TiO₂ hybrid membranes prepared by blending method, most of CS/TiO₂ nanocomposite membranes prepared by in situ sol-gel process exhibited higher permeation flux and separation factor under the identical conditions. Among all the prepared membranes, CS/TiO₂ nanocomposite membrane containing 6 wt% TiO₂ exhibited the best pervaporation performance, whose averaged permeation flux and separation factor were 0.340 kg m⁻² h⁻¹ and 196 for 90 wt% aqueous solution of ethanol at 80 °C, respectively.     

Photocatalytic properties of TiO2 sol-gel modified nanocomposite films

TiO₂ nanocomposite films with different concentrations of TiO₂ MT-150A nanoparticles were immobilized on glass substrates using a dip coating process. The crystalline structure and surface chemical state of nanocomposite film properties were examined by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. The specific surface area and morphology of TiO₂ MT-150A nanoparticles were evaluated by the BET method and Field Emission Scanning Electron Microscopy (FE-SEM). The photocatalytic activities of films were evaluated by the methyl orange decoloring rate. XPS measurements showed that the oxygen amount (%) was related to the film composition. The composite film with 10 g/L MT-150A loading yielded the highest amount of surface oxygen (26.82%) and TiO₂ rutile showed the lowest amount of surface oxygen (13.67%) in the form of surface hydroxyl groups. The remaining oxygen was identified as lattice oxygen. In addition, the nanocomposite film with 10 g/L MT-150A loading yielded the highest photocatalytic activity.     

Synthesis and dielectric properties of polyaniline/titanium dioxide nanocomposites

Two series of polyaniline–TiO₂ nanocomposite materials were prepared in base form by in situ polymerization of aniline with inorganic fillers using TiO₂ nanoparticles (P25) and TiO₂ colloids (Hombikat), respectively. The effect of particle sizes and contents of TiO₂ materials on their dielectric properties was evaluated. The as-synthesized polyaniline–TiO₂ nanocomposite materials were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR), thermal analysis (DTA/TGA), and X-ray diffraction (XRD). Dielectric properties of polyaniline–TiO₂ nanocomposites in the form of films were measured at 1 KHz–1 MHz and a temperature range of 35–150 °C. Higher dielectric constants and dielectric losses of polyaniline–TiO₂ nanocomposites than those of neat PANI were found. PANI–TiO₂ nanocomposites derived from P25 exhibited higher dielectric constants and losses than those from Hombikat TiO₂ colloids. Electrical conductivity measurements indicate that the conductivity of nanocomposites is increased with TiO₂ content. The dielectric properties and conductivities are considered to be enhanced due to the addition of TiO₂, which might induce the formation of a more efficient network for charge transport in the base polyaniline matrix.     

Efficient preparation of hybrid nanocomposite coatings based on poly(vinyl alcohol) and silane coupling agent modified TiO2 nanoparticles

In the present investigation, at first, the surface of titanium dioxide (TiO₂) nanoparticles was modified with γ-aminopropyltriethoxy silane as a coupling agent. Then a new kind of poly(vinyl alcohol)/titanium dioxide (PVA/TiO₂) nanocomposites coating with different modified TiO₂ loading were prepared under ultrasonic irradiation process. Finally, these nanocomposites coating were used for fabrication of PVA/TiO₂ films via solution casting method. The resulting nanocomposites were fully characterized by Fourier transform infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD), thermogravimetric analysis/derivative thermal gravimetric (TGA/DTG), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The TEM and SEM results indicated that the surface modified nanoparticles were dispersed homogeneously in PVA matrix on nanoscale and based on obtained results a possible mechanism was proposed for ultrasonic induced nanocomposite fabrication. TGA confirmed that the heat stability of the nanocomposite was improved. UV–vis spectroscopy was employed to evaluate the absorbance and transmittance behavior of the PVA/TiO₂ nanocomposite films in the wavelength range of 200–800 nm. The results showed that this type of films could be used as a coating to shield against UV light.     

Effects of annealing temperature on the photocatalytic activity of N-doped TiO2 thin films

The effects of annealing temperature on the photocatalytic activity of nitrogen-doped (N-doped) titanium oxide (TiO₂) thin films deposited on soda-lime-silica slide glass by radio frequency (RF) magnetron sputtering have been studied. Glancing incident X-ray diffraction (GIAXRD), Raman spectrum, scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV-vis spectra were utilized to characterize the N-doped TiO₂ thin films with and without annealing treatment. GIAXRD and Raman results show as-deposited N-doped TiO₂ thin films to be nearly amorphous and that the rutile and anatase phases coexisted when the N-doped TiO₂ thin films were annealed at 623 and 823 K for 1 h, respectively. SEM microstructure shows uniformly close packed and nearly round particles with a size of about 10 nm which are on the slide glass surface for TiO₂ thin films annealed at 623 K for 1 h. AFM image shows the lowest surface roughness for the N-doped TiO₂ thin films annealed at 623 K for 1 h. The N-doped TiO₂ thin films annealed at 623 K for 1 h exhibit the best photocatalytic activity, with a rate constant (k_a) of about 0.0034 h⁻¹.     

Fabrication of polyimide/titania nanocomposites containing benzimidazole side groups via sol–gel process

In recent years, polyimide (PI) hybrid materials have received considerable attention owing to the dramatic enhancements over their pristine state in thermal stabilities, mechanical properties and other special features by introducing only a small fraction of inorganic additives. In this investigation, hybrid nanocomposite films of titanium dioxide (TiO₂) in PI were successfully fabricated by an in situ sol–gel process starting from tetraethyl orthotitanate in the solution of poly(amic acid) in N,N-dimethylacetamide. Neat PI was prepared from the polymerization of 2-(3,5-diaminophenyl)-benzimidazole and pyromellitic dianhydride. The hybrid films were obtained by the hydrolysis–polycondensation of moisture-sensitive titania precursor in poly(amic acid) solution, followed by the elimination of solvents and imidization process. The chelating agent, acetylacetone, was used to reduce the gelation rate of titanium alkoxide. The complete imidization temperature of the poly(amic acid) was delayed; furthermore, the thermal stability of PI was enhanced through the incorporation of the inorganic moieties in the hybrid materials. The chemical and morphological structures of the hybrid materials were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, field emission scanning electron microscopy and transmission electron microscopy. The results show that the TiO₂ particles are well dispersed in the PI matrix with particle size between 15 and 30 nm in diameter.     

Effects of titania content and plasma treatment on the interfacial adhesion mechanism of nano titania-hybridized polyimide and copper system

Nano-titania (TiO₂) incorporated into polyimide (PI) matrix can significantly enhance the adhesion strength for PI/TiO₂ hybrid film and copper system. Surface modifications by various plasma treatments (Ar, Ar/N₂ and Ar/O₂) were also applied in this study to improve the adhesion strength. The Ar/N₂ plasma treatment is regarded as the more effective way in promoting the adhesion strength. The maximum adhesion value of 9.53 N/cm was obtained for the PI/TiO₂-1 wt% hybrid film with Ar/N₂ plasma treatment. It is enhanced about 10 times as large as pristine PI. Furthermore, by Ar/O₂ plasma treatment, a weak boundary of copper oxide was formed at the interlayer between PI/TiO₂ hybrid film and copper which decreases the adhesion strength. The effects of plasma treatment and content of nanosized TiO₂ on the adhesion strength between PI/TiO₂ hybrid film and copper system were studied. Atomic force microscope and contact angle analyses were used to measure the changes in surface morphology and surface energy as a result of plasma treatment. Besides, the interfacial states of peeled-off polymer side and copper side were investigated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Based on the result of XPS spectra, the peeled-off failure mode between PI/TiO₂ hybrid film and copper was proposed in this study.     

Electrochemical Polymerization of Thiophene and Poly(3-hexyl)thiophene,Nanocomposites with TiO2, and Corrosion Protection Behaviors

Thiophene, 3-hexylthiophene, and their nanocomposites with TiO₂ were electropolymerized on Al1050 electrode by chronoamperometric technique. Different concentrations of thiophene and 3-hexylthiophene homopolymers and their nanocomposites with TiO₂ (2% in total content) were characterized by attenuated total reflection Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersion X-ray analysis, and electrochemical impedance spectroscopy. The anticorrosion tests for homopolymers and nanocomposite films were examined on Al1050 in 3.5% NaCl solution. Poly(3-hexylthiophene)/TiO₂ nanocomposite films gave the highest protection efficiency of 98% because the amount of defects was much lower than that for the poly(3-hexylthiophene), polythiophene, and polythiophene/TiO₂ films.     

Electrophoretic deposition of nanocrystalline TiO2 films on Ti substrates for use in flexible dye-sensitized solar cells

Nanocrystalline TiO₂ films were prepared on flexible Ti-metal sheets by electrophoretic deposition followed by chemical treatment with tetra-n-butyl titanate (TBT) and sintering at 450 °C. X-ray diffraction (XRD) analysis indicates that TBT treatment led to the formation of additional anatase TiO₂, which plays an important role in improving the interconnection between TiO₂ particles, as well as the adherence of the film to the substrate, and in modifying the surface properties of the nanocrystalline particles. The effect of TBT treatment on the electron transport in the nanocrystalline films was studied by intensity-modulated photocurrent spectroscopy (IMPS). An increase in the conversion efficiency was obtained for the dye-sensitized solar cells with TBT-treated nanocrystalline TiO₂ films. The cell performance was further optimized by designing nanocrystalline TiO₂ films with a double-layer structure composed of a light-scattering layer and a transparent layer. The light-scattering effect of the double-layer nanocrystalline films was evaluated by diffuse reflectance spectra. Employing the double-layer nanocrystalline films as the photoelectrodes resulted in a significant improvement in the incident photo-to-current conversion efficiency of the corresponding cells due to enhanced solar absorption by light scattering. A high conversion efficiency of 6.33% was measured under illumination with 100 mW cm⁻² (AM 1.5) simulated sunlight.     

Synthesis and characterization of mesoporous TiO2 nanostructured films prepared by a modified sol-gel method for application in dye solar cells

Anatase TiO₂ colloidal dispersions were obtained by hydrothermal synthesis at 200 °C from titanium isopropoxide gels modified with acetic acid in the presence of a non-ionic surfactant. Absolute ethanol, anhydrous terpineol and ethyl cellulose were added to this anatase dispersion resulting in a 23 wt% TiO₂ paste. Mesoporous films for application as working electrodes in dye-sensitized solar cells were prepared by the screen-printing method, yielding reproducible films with thicknesses about 10 μm and desired porosity levels in a single printing operation. An average energy conversion efficiency of 5.2%, and a fill factor of 0.66 were achieved with anatase particle sizes ranging between 15 and 20 nm. The reproducibility of the results was confirmed by electrochemical impedance spectroscopy analysis.     

Fabrication of a New Polyimide/Titania (TiO2) Nanocomposite Thin Film by the Sol-Gel Route

Polyimide/titania nanocomposite (PI/TiO₂ NC) was successfully fabricated through the in situ formation of TiO₂ within a PI matrix by the sol-gel process. FT-IR and XRD results confirmed the formations of the TiO₂ in the PI matrix. Transmission electron microscopy of the NC10% showed that the TiO₂ phase was well dispersed in the polymer matrix. The mechanical properties of the NC films were increased and elongation at break decreased with increasing TiO₂ content. Thermogravimetric analysis results revealed that the decomposition temperature of hybrid materials was increased with an increase in the content of TiO₂ nanoparticles within the NC films.     

Microstructure and properties of polyimide/poly(vinylsilsesquioxane) hybrid composite films

Polyimide (PI)/poly(vinylsilsesquioxane) (PVSSQ) (PI/PVSSQ) hybrid composite films were prepared from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA)-4,4′-oxydianiline (ODA) polyamic acid and triethoxyvinylsilane (TEVS or VSSQ) via sol-gel process and thermal imidization. The presence of the PVSSQ showed a remarkable effect on the microstructure and properties of the polyimide based hybrid films. The transparency of the hybrid films decreased with increasing the content of the PVSSQ. The compatibility and interfacial interaction of the hybrid composites were evaluated by scanning electron microscope (SEM) and atomic force microscope (AFM), respectively. The PI/PVSSQ hybrids showed nanocomposite formation when the contents of PVSSQ was less than 20 wt%. It was found that the surface topography was influenced by the composition of the PVSSQ. Incorporating of the PVSSQ increased the thermal stability and T_g of hybrid composites. The dielectric constant of the hybrid composites was reduced by adding PVSSQ up to a certain content, showed a minimum and then found to be increased. The dielectric constant values of the hybrid composites ranged from 2.59 to 3.78. The presence of the PVSSQ also showed significant effects on the mechanical properties of the polyimide films.     

TiO2 films prepared by micro-plasma oxidation method for dye-sensitized solar cell

Nanocrystalline TiO₂ films are widely investigated as the electrodes of dye-sensitized solar cell(s) with different preparation methods. In this paper, thin titanium dioxide films have been prepared on titanium plates by the micro-plasma oxidation method in the sulfuric acid solution. The thin TiO₂ films were sensitized with a cis-RuL₂(SCN)₂·2H₂O (L = cis-2,2′-bipyridine-4,4′-dicarboxylic acid) ruthenium complex and implemented into a dye-sensitized solar cell configuration. The influence of reaction current density (10, 15, 20, 25 and 30 A dm⁻²) on the structural and the surface morphology of the films was investigated by X-ray diffraction, scanning electron microscopy, atom force microscopy and X-ray photoelectricity spectroscopy. Impedance analysis for dye-sensitized solar cells was carried out by electrochemical impedance spectroscopy. The results show that the rise of current density leads to the increase in the amount of rutile and the thickness of the TiO₂ film, which makes the TiO₂ films have different photovoltages and photocurrents. The relatively higher photoelectricity properties were obtained in the TiO₂ films prepared at a current density of 20 A dm⁻². The open-circuit voltage and the short-circuit current are 605 mV and 165 μA cm⁻², respectively.     

Preparation of high solids content nano-titania suspensions to obtain spray-dried nanostructured powders for atmospheric plasma spraying

Nanosized TiO₂ powder with an average primary size of ∼20 nm and surface area of ∼50 m²/g (Aeroxide^® P25, Degussa-Evonik, Germany) was used as starting material. A colloidal titania suspension from the same supplier was also used (W740X). The dispersing conditions were studied as a function of pH, dispersant content, and solids loading. Well-dispersed TiO₂ nanosuspensions with solids contents up to 30 vol.% (62 wt%) were obtained by dispersing the powder with 4 wt% PAA. Suspensions with solids contents as high as 35 vol.% were prepared by adding the TiO₂ nanoparticles to the TiO₂ colloidal suspension under optimised dispersing conditions.TiO₂ powder reconstitution was performed by spray drying both types of nanosuspensions to obtain free-flowing micrometre-sized nanostructured granules. The spray-dried nanostructured TiO₂ granules were deposited on austenitic stainless steel coupons using atmospheric plasma spraying. Coating microstructure and phase composition were characterised using scanning electron microscopy and X-ray diffraction techniques.     

Mesoporous polyaniline or polypyrrole/anatase TiO2 nanocomposite as anode materials for lithium-ion batteries

A functional composite as anode materials for lithium-ion batteries, which contains highly dispersed TiO₂ nanocrystals in polyaniline matrix and well-defined mesopores, is fabricated by employing a novel one-step approach. The as-prepared mesoporous polyaniline/anatase TiO₂ nanocomposite has a high specific surface area of 224 m² g⁻¹ and a predominant pore size of 3.6 nm. The electrochemical performance of the as-prepared composite as anode material is investigated by cyclic voltammograms and galvanostatic method. The results demonstrate that the polyaniline/anatase nanocomposite provides larger initial discharge capacity of 233 mAh g⁻¹ and good cycle stability at the high current density of 2000 mA g⁻¹. After 70th cycles, the discharge capacity is maintained at 140 mAh g⁻¹. The excellent electrochemical performance of the polyaniline/TiO₂ nanocomposite is mainly attributed to its special structure. Furthermore, it is accessible to extend the novel strategy to other polymer/TiO₂ composites, and the mesoporous polypyrrole/anatase TiO₂ is also successfully fabricated.     

Improved performance of dense TiO2/CdSe coupled thin films by low temperature process

Dense TiO₂ and TiO₂/CdSe coupled nanocrystalline thin films were synthesized onto ITO coated glass substrate by chemical route at relatively low temperature (≤100 °C). TiO₂ films were nanocrystalline and crystallinity disappears after CdSe deposition as evidenced by X-ray powder diffraction. Surface morphology and physical appearance of films were studied from SEM and actual photo-images, reveals dense nature of TiO₂ (10-12 nm spherical grains, faint violet) and CdSe (80-90 nm spherical grains, deep brown), respectively. Presence of two absorption edges in UV spectra implies existence of separate phases rather than composite formation. TiO₂ film was found to have higher water contact angle (71°) than TiO₂/CdSe (61°) and CdSe (56°). I-V and stability tests of photo-electrochemical cells were performed with TiO₂ and TiO₂/CdSe film electrodes (under light of illumination intensity 80 mW/cm²) in lithium iodide as an electrolyte using two-electrode system.     

Inorganic-organic hybrid membranes with anhydrous proton conduction prepared from tetramethoxysilane/methyl-trimethoxysilane/trimethylphosphate and 1-ethyl-3-methylimidazolium-bis (trifluoromethanesulfonyl) imide for H2/O2 fuel cells

Anhydrous proton-conducting inorganic-organic hybrid membranes were prepared by sol-gel process with tetramethoxysilane/methyl-trimethoxysilane/trimethylphosphate and 1-ethyl-3-methylimidazolium-bis (trifluoromethanesulfonyl) imide [EMI][TFSI] ionic liquid as precursors. These hybrid membranes were studied with respect to their structural, thermal, proton conductivity, and hydrogen permeability properties. The Fourier transform infrared spectroscopy (FT-IR) and ³¹P, ¹H, and ¹³C nuclear magnetic resonance (NMR) measurements have shown good chemical stability, and complexation of PO(OCH₃)₃ with [EMI][TFSI] ionic liquid in the studied hybrid membranes. Thermal analysis including TG and DTA confirmed that the membranes were thermally stable up to 330 °C. Thermal stability of the hybrid membranes was significantly enhanced by the presence of inorganic SiO₂ framework and high stability of [TFSI] anion. The effect of [EMI][TFSI] ionic liquid addition on the microstructure of the membranes was studied by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX) micrographs and no phase separation at the surfaces of the prepared membranes was observed and also homogeneous distribution of all elements was confirmed. Proton conductivity of all the prepared membranes was measured from −20 °C to 150 °C, and high conductivity of 5.4 × 10⁻³ S/cm was obtained for 40 wt% [EMI][TFSI] doped 40TMOS-50MTMOS-10PO(OCH₃)₃ (mol%) hybrid membrane, at 150 °C under anhydrous conditions. The hydrogen permeability was found to decrease from 1.61 × 10⁻¹¹ to 1.39 × 10⁻¹² mol/cm s Pa for 40 wt% [EMI][TFSI] doped hybrid membrane as the temperature increases from 20 °C to 150 °C. For 40 wt% [EMI][TFSI] doped hybrid membrane, membrane electrode assemblies were prepared and a maximum power density value of 0.22 mW/cm² at 0.47 mA/cm² as well as a current density of 0.76 mA/cm² were obtained at 150 °C under non-humidified conditions when utilized in a H₂/O₂ fuel cell.     

Preparation and characterization of CeO2/TiO2 nanoparticles by flame spray pyrolysis

Nanocrystalline TiO₂, CeO₂ and CeO₂-doped TiO₂ have been successfully prepared by one-step flame spray pyrolysis (FSP). Resulting powders were characterized with X-ray diffraction (XRD), N₂-physisorption, Transmission Electron Microscopy (TEM) and UV-Vis spectrophotometry. The TiO₂ and CeO₂-doped TiO₂ nanopowders were composed of single-crystalline spherical particles with as-prepared primary particle size of 10-13 nm for Ce doping concentrations of 5-50 at%, while square-shape particles with average size around 9 nm were only observed from flame-made CeO₂. The adsorption edge of resulting powder was shifted from 388 to 467 nm as the Ce content increased from 0 to 30 at% and there was an optimal Ce content in association with the maximum absorbance. This effect is due to the insertion of Ce^3+/4+ in the TiO₂ matrix, which generated an n-type impurity band.