A new modified silicone–TiO2 polymer composite film and its photocatalytic degradation

The photodegradation of the silicone surfactant–TiO₂ composite films was characterized by FTIR, Raman spectroscopy, and scanning electron microscope. After photocatalytic degradation, the FTIR Si? O? Si peak intensity of the composite film remained unchanged, implying no cleavage of Si? O? Si bond. The above Si? O? Si peak intensity is sensitive to the polyoxyethylene chain length of the composite. The PEG10000‐silicone composite is more resistant to photodegradation than those composites with lower molecular weight of constituent PEGs. The wetting rates of the silicone surfactant–TiO₂ composites showed that modified silicone composite films exhibited hydrophobic nature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3341–3344, 2006     

Solid‐phase photocatalytic degradation of polystyrene with TiO2/Fe(St)3 as catalyst

A novel photodegradable TiO₂‐Fe(St)₃‐polystyrene (TiO₂‐Fe(St)₃‐PS) nanocomposite was prepared by embedding TiO₂ and Fe(St)₃ into the commercial polystyrene. Ferric stearate was added into polymer as cocatalyst in order to improve the dispersion in polystyrene and photocatalytic efficiency of TiO₂ nanoparticles. Solid‐phase photocatalytic degradation of the TiO₂‐Fe(St)₃‐PS nanocomposite was carried out in an ambient air at room temperature under ultraviolet lamp. The properties of TiO₂‐Fe(St)₃‐PS composite film were compared with that of the pure PS film and the TiO₂‐PS composite film, through weight loss monitoring, scanning electron microscope, gel permeation chromatogram, and FTIR spectroscopy. The photodegradation efficiency of TiO₂‐Fe(St)₃‐PS composite film was higher than that of the pure PS film and the TiO₂‐PS composite film under the UV light irradiation. The average molecular weight (M_w) of TiO₂‐Fe(St)₃‐PS composite film decreased 63.08%, and the number of average molecular weight (M_n) decreased 79.49% after UV light irradiation for 480 h. Photo‐oxidation leads to an increase in the low molecular weight fraction by chain scission, thereby facilitating biodegradation. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

TiO2‐kaolin‐PE composite film: A study based on photocatalytic degradation and biodegradation

A novel photodegradable and biodegradable polyethylene (PE) film was prepared through a melt blending technique, where nano‐TiO₂ and common kaolin were used as the photocatalyst and biodegradable promoter showing improved degradable efficiency of the waste PE. The photo‐degradation of the composite film was investigated by weight loss monitoring, attenuated total reflection–fourier transformed infrared spectroscopy (ATR–FTIR), and scanning electron microscopy. The aerobic biodegradation of the residue films after photodegradation was investigated by analysis of evolved carbon dioxide of films in aquatic test systems according to the international standards (ISO 14852, 1999). The results showed that the weight loss of as‐prepared photo‐ and biodegradable composite film reached 26.8% after 240 h of UV light irradiation. The big cavities formed not only on the film surface but also inside the bulk film, together with the chalking phenomenon taking place. The biodegradation results revealed that the addition of kaolin enhanced the degradation of UV‐light treated TiO₂‐PE films. The prepared PE based composite films showed promising application as novel photo‐biodegradable environment‐harmless materials. In addition, a degradation mechanism for this composite film was also discussed. POLYM. COMPOS., 37:2353–2359, 2016. © 2015 Society of Plastics Engineers     

The synthesis and morphology characteristic study of BAO-ODPA polyimide/TiO2 nano hybrid films

Hybrid nanocomposite films of titanium dioxide (TiO₂) in polyimide (PI) from 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole (BAO) and 4,4′-oxydiphthalic anhydride (ODPA) have been successfully fabricated by an in situ sol-gel process. These nanocomposite films exhibit fair good optical transparency up to 40 wt% of TiO₂ content. X-ray diffraction spectroscopy shows three sharp peaks in pure BAO-ODPA PI. It results from the intermolecular regularity. However, the intermolecular regularity in the hybrid film is disrupted by the introduction of TiO₂ nanoparticles with no sharp peak in XRD spectra. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) results confirm the formation of TiO₂ particles in PI matrix. The surface Ti content is much lower than the theoretical bulk content in all hybrid films. The ratio of the former to the latter increases with the TiO₂ content and levels off at TiO₂ wt%≥20. Transmission electron microscope (TEM) images show that the TiO₂ phase is well dispersed in the polymer matrix. The size of the TiO₂ phase increases from 10 to 40 nm when the TiO₂ content is 5-30 wt%, respectively.     

Structure,electrical and optical properties of (PVA/LiAsF6) polymer composite electrolyte films

In this work, Li⁺ ion conducting polymer composite electrolyte films (PECs) were prepared based on poly (vinyl alcohol) (PVA), lithium hexafluoro arsenate (LiAsF₆), and ceramic filler TiO₂ using solution cast technique. The XRD and FTIR spectra were used to determine the complexation of the PVA polymer with LiAsF₆ salt. The ionic conductivities of the (PVA + LiAsF₆) and (PVA + LiAsF₆ + TiO₂) films have been determined by the A.C. impedance measurements in the temperature range 320–440 K. The maximum conductivity was found to be 5.10 × 10^?4 S cm^?1 for PVA:LiAsF₆ (75:25) + 5 wt% TiO₂ polymer composite film at 320 K. The calculation of Li⁺ ion transference number was carried out by the combination of A.C. impedance and D.C. polarization methods and is found to be 0.52 for PVA:LiAsF₆ (75:25) + 5 wt% TiO₂ film. Optical properties such as direct energy gap, indirect energy gap, and optical absorption edge values were investigated in pure PVA and salt complexed PVA films from their optical absorption spectra in the wavelength range of 200–600 nm. The absorption edge was found at 5.76 eV for undoped film, while it is observed at 4.87 and 4.70 eV for 20 and 25 wt% LiAsF₆ doped films, respectively. The direct band gaps for these undoped and salt doped PVA films were found to be 5.40, 5.12, and 4.87 eV, respectively, whereas the indirect band gaps were determined as 4.75, 4.45, and 4.30 eV. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Visible light photocatalytic activity of TiO2/heat‐treated PVC film

BACKGROUND: Semiconductor TiO₂ has been investigated extensively due to its chemical stability, nontoxicity and inexpensiveness. However, the wide band gap of anatase TiO₂ (about 3.2 eV) only allows it to absorb UV light. TiO₂ nanoparticles modified by conditional conjugated polymers show excellent photocatalytic activity under visible light. However, these conjugated polymers are not only expensive, but also difficult to process. Polyvinyl chloride (PVC) was heat‐treated at high temperature to remove HCl and a C?C conjugated chain structure was obtained. When TiO₂ nanoparticles were dispersed into the conjugated polymer film derived from PVC, this composites film exhibited high visible light photocatalytic activity. RESULTS: The photocatalytic activity of TiO₂/heat‐treated PVC (HTPVC) film was investigated by degrading Rhodamine B (RhB) under visible light irradiation. The photodegradation of RhB follows apparent first‐order kinetics. The rate constants of RhB photodegradation in the presence of the TiO₂/HTPVC films with different mass content of TiO₂ are 16–56 and 4–14 times that obtained in the presence of the pure HTPVC and TiO₂/polymethyl methacrylate (PMMA) composite film, respectively. The TiO₂/HTPVC film showed excellent photocatalytic activity and stability after 10 cycles under visible light irradiation. CONCLUSION: TiO₂/HTPVC film exhibits high visible light photocatalytic activity and stability. Copyright © 2012 Society of Chemical Industry     

Enhanced photochromism of heteropolyacid/polyvinylpyrolidone composite film by TiO2 doping

Novel composite film was synthesized by TiO₂ doping into phosphomolybdic acid (PMoA)/polyvinylpyrrolidone (PVP) system. The influence of TiO₂ doping on its microstructure and photochromic properties was investigated via atomic force microscopy, transmission electron microscope, Fourier transform infrared spectroscopy (FT‐IR), ultraviolet–visible spectra, and X‐ray photoelectron spectroscopy (XPS). After TiO₂ doping, the surface of TiO₂/PMoA/PVP composite film changed to rough from smooth, and the particle size significantly increased. The FT‐IR results verified that the basic structure of PMoA and PVP were not destroyed in the composite films. The non‐bonded interaction between the acid and polymer was strengthened by TiO₂ doping. Irradiated with UV light, composite films changed from colorless to blue. The TiO₂/PMoA/PVP composite film exhibited a strong photochromic effect and faster bleaching reaction than that of PMoA/PVP film. XPS results indicated that the amount of PMoA in photo‐reductive reaction was increased after TiO₂ doping, which resulted in the photochromic efficiencies enhanced. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41583.     

Titanium dioxide photocatalysed oxidation of plasticisers in thin poly(vinyl chloride) films

Abstract

A closed system incorporating FTIR continuous monitoring and GC-MS sampling has been developed to study the generation under UVA illumination of volatile photodegradation products from model plasticised and TiO₂ pigmented films. The presence of the plasticiser dibutyl adipate (DBA), at levels of 0-88 phr, has been shown to slow the onset of yellowing of PVC caused by the formation of polyene sequences through photodegradation of the polymer matrix. However, increasing the plasticisation increases the amount of volatile byproducts emitted under intense UVA illumination as a result of TiO₂ catalysed photodegradation. The rate of CO₂ production from irradiated films increases linearly by up to a factor of 21 as the concentration of DBA is raised from 0 to 88 phr. This increase in the rate of CO₂ production suggests increasing photoactivity within the film and this, accompanied by a decreased yellowing rate of the polymer backbone, implies that the plasticiser is photo-oxidised in preference to the polymer matrix. In addition, small quantities of organic molecular fragments (up to a maximum of ~10 mumol m -² ) are released into the gas phase above the films and have been trapped using adsorption tubes. The molecular structures of the emitted species form an homologous series, the parent of which is the plasticiser, each with one fewer carbon atoms. All the fragments are produced at similar levels suggesting the mode of fragmentation is via random scission. The production of volatile organic carbon compounds (VOCs) peaks after 1 h irradiation, which corresponds to the initial rapid photo-oxidation of plasticiser moieties bound to the TiO₂ surface. The VOC emissions account for only ~3% of the total carbon emission with ~97% accounted for by CO₂, suggesting that the major breakdown pathway is via complete oxidation with the majority of retained molecular fragments within the irradiated polymer film being subsequently oxidised. The efficiency of such oxidation is similar for each fragment as determined by separate complete oxidation studies over irradiated pure TiO₂ films. In each case the major product is CO₂ with only small quantities of other VOCs being produced.     

Electrochemical polymerization and characterization of a poly(azulene)-TiO<Subscript>2</Subscript> nanoparticle composite film

A poly(azulene)-TiO₂ composite film (PAz-TiO₂) was synthesized electrochemically by oxidation of azulene in an electrolyte medium containing TiO₂ nanoparticles. Polymerization was performed under magnetic stirring in an acetonitrile solution containing tetrabutylammonium hexafluorophosphate as the electrolyte salt. Influence of the concentration of TiO₂ in the reaction suspension on the electrochemical and optical properties and on the structure of the composite films was studied by cyclic voltammetry, ex situ Raman and FTIR reflection spectroscopy and in situ UV–vis and FTIR spectroelectrochemical techniques. Morphology of the composite films was studied by Scanning Electron Microscopy and the amount and distribution of the TiO₂ nanoparticles within the polymeric matrix by Inductively Coupled Plasma Mass Spectrometry with laser ablation. Addition of TiO₂ in the reaction suspension had a small catalytic activity for the polymerization of Az. Inclusion of TiO₂ nanoparticles in PAz did not affect the voltammetric behavior or the chemical structure of the formed polymer films. However, a different chain conformation and morphology of the film was formed when synthesized in presence of TiO₂ compared to the plain PAz film. It was also found that the film morphology was more homogeneous when the concentration of TiO₂ was ≥10 mM in the polymerization solution than films polymerized without any TiO₂.     

Improvement of photostability and thermal stability of PVC by carbon quantum dots loaded on TiO2

Titanium dioxide (TiO₂) has a strong oxidation effect when absorbing ultraviolet light. Therefore, when TiO₂ is used as a light stabilizer in polyvinyl chloride (PVC), it will cause the photodegradation of PVC. Herein, carbon quantum dots (CQDs) coated TiO₂ composite (TiO₂@CQDs) was prepared by a one-step hydrothermal method. The prepared TiO₂@CQDs were characterized by transmission electron microscopy (TEM), UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The photostability of PVC film containing TiO₂@CQDs was investigated via photodegradation conductivity test, weight loss rate test, and ultraviolet aging test. Due to the down-conversion effect of CQDs under ultraviolet light, its existence can alleviate the photoaging of PVC. In addition, the thermal stability of PVC containing TiO₂@CQDs was studied by conductivity tests and oven thermal aging tests. The presence of CQDs significantly improved the thermal stability of PVC. Meanwhile, the HCl absorption capacity of CQDs could reach 30.8 mg/g_cat. According to the DFT calculations, this high absorption capacity is attributed to the HCl immobilization effect via forming hydrogen bonds between HCl and the keto oxygen, carboxyl keto oxygen in CQDs. The hydroxyl group in CQDs could also combine ZnCl₂ by forming a coordination bond.     

Surface analysis of aminated polypropylene films as an adhesion promoter to polycarbonate film

The surface composition of aminated polypropylene films (PP‐g‐NH₂) and their adhesion to polycarbonate (PC) film were evaluated. The detection of amine groups on PP‐g‐NH₂ surfaces was obtained by X‐ray photoelectron spectroscopy (XPS). Contact angle measurements showed a decreased in the polarity on PP‐g‐NH₂ surface The adhesion between laminated films of PP‐g‐NH₂ and PC was evaluated by T‐peel test and optical microscopy. PC deposited on the PP‐g‐NH₂ surfaces was confirmed by FTIR‐ATR and SEM analysis of delaminated films, which is an indicative of an interaction between reactive sites of each polymer. The adhesion performance between PC and PP was improved by using amine modified polypropylene (PP‐g‐NH₂). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Evaluation of the removal of n-butanol vapor by the poly(lactic acid)-zeolite-TiO2 composite and formation of by-products

The use of polymeric films incorporated with zeolite-TiO₂ composites associated with UV radiation can be an alternative in the removal of volatile organic compounds (VOCs) through the adsorption and photodegradation processes. This study produced poly(lactic acid) (PLA) films incorporated with 13× zeolite, TiO₂, and 13×-TiO₂ zeolite composite to remove n-butanol and evaluate the by-products generated in the process. The results showed that 13× zeolite and TiO₂ added individually or as a composite to PLA, gave the polymer matrix a significant increase in the removal capacity of n-butanol. The best performance was presented by the zeolite-TiO₂, composite, confirming a synergistic effect. However, the formation of CO and CO₂ exceeded the expected values, with the verification that the polymeric matrix underwent photodegradation action by TiO₂. The polymeric film only containing zeolite is the most suitable for the removal of VOCs, as it did not present degradation of the PLA, generating a lower concentration of by-products.     

Solid-phase photocatalytic degradation of polystyrene with modified nano-TiO2 catalyst

A novel photodegradable polystyrene-grafted-TiO₂ (PS-g-TiO₂) nanocomposite was prepared by embedding the grafted-TiO₂ into the commercial polystyrene. Solid-phase photocatalytic degradation of the PS-g-TiO₂ nanocomposite was carried out in ambient air at room temperature under ultraviolet lamp and/or sunlight irradiation. The properties of composite film were compared with those of the pure PS film by methods such as weight loss measurement, scanning electron microscope (SEM), gel permeation chromatogram (GPC), X-ray photoelectron spectroscopy (XPS), FT-IR spectroscopy, and UV-vis spectroscopy. The results show that the photo-induced degradation of PS-g-TiO₂ composite film is significantly higher than that of pure PS film. The weight loss of composite film reached 31.9%, average molecular weight (M_w) of composite film decreased by 53.1%, and the number average molecular weight (M_n) decreased by 73.2% after 396 h of UV-light irradiation. FT-IR analysis and weight loss indicated that the benzene rings in PS-matrix of composite film were cleaved during UV-light irradiation. The photocatalytic degradation mechanism of the films is briefly discussed.     

P(VDF-HFP)-based micro-porous composite polymer electrolyte prepared by in situ hydrolysis of titanium tetrabutoxide

A micro-porous composite polymer electrolyte (MCPE) was prepared in situ by adding TiO₂ nanoparticles from the hydrolysis of titanium tetrabutoxide to a solution of poly(vinylidenefluoride-co-hexafluoropropylene) [P(VDF-HFP)] copolymer. The prepared microporous polymer films (MCPFs) were characterized by scanning electronic microscopy, X-ray diffraction, thermogravimetric analysis, FT-IR and electrochemical interface resistance. After the addition of TiO₂ nanoparticles the polarity of CF₂ groups in the polymer chains and the crystallinity of the MCPFs decreased. When the composite polymer film contained 8.5 wt% of TiO₂ nanoparticles the MCPE exhibited excellent electrochemical properties such as high ionic conductivity, up to 2.40 × 10⁻³ S cm⁻¹ at room temperature.     

Polystyrene photodegradation with a novel titanium dioxide/poly(ethylene oxide)/methyl linoleate paint photocatalyst system

The photodegradation of a polystyrene (PS) film was performed by a titanium dioxide (TiO₂)/poly(ethylene oxide) (PEO)/methyl linoleate (ML) paint photocatalyst system. The PS surface was catalytically photodegraded by the TiO₂/PEO component, and a conjugated carbon–carbon double bond was partially produced. A crosslinking reaction occurred between the PS carbon–carbon double bond and radical spices; as a result, the photodegradation diffusion into the inner region was blocked. The additional ML component certainly blocked the crosslinking reaction and accelerated the photodegradation rate. The fraction of less than 10,000 molecular weight of the 4‐h‐photodegaraded film with the TiO₂/PEO/ML paint was 15.1%, and its photodegradation yield increased four times compared with that with the TiO₂/PEO one. The weight loss values of the photodegraded PS part were 9.9, 10.7, and 11.7% at 4, 8, and 12 h, respectively, and gradually increased with increasing irradiation time. Some part of the film was violently photodegraded by the paint, and its photocatalytic effect lasted. The ML was graft‐polymerized into the film, and a phase separation was caused. The photodegradation behavior between the 0.05‐ and 0.1‐mm films was remarkably different; this showed that the diffusion of the ML radical was affected by the film thickness. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis,characterisation and flame,thermal and electrical properties of poly (<Emphasis Type="Italic">n</Emphasis>-butyl methacrylate)/titanium dioxide nanocomposites

Nanocomposites based on poly (n-butyl methacrylate) (PBMA) with various concentrations of titanium dioxide (TiO₂) nanoparticles were synthesised by in situ free radical polymerisation method. The formation of nanocomposite was characterised by FTIR, UV, XRD, DSC, TGA, impedance analyser and flame retardancy measurements. FTIR and UV spectrum ascertained the intermolecular interaction between nanoparticles and the polymer chain. The XRD studies indicated that the amorphous region of PBMA decreased with the increase in content of metal oxide nanoparticles. The SEM revealed the uniform dispersion of nanoparticles in the polymer composite. The DSC and TGA studies showed that the glass transition temperature and thermal stability of the nanocomposites were increased with the increase in the concentration of nanoparticles. The conductivity and dielectric properties of nanocomposites were higher than pure PBMA and the maximum electrical property was observed for the sample with 7 wt% TiO₂. As the concentration of nanoparticles increased above 7 wt%, the electrical property of nanocomposite was decreased owing to the agglomeration of nanoparticles in the polymer. Nanoparticles could impart better flame retardancy to PBMA/TiO₂ composite and the flame resistance of the materials improved with the addition of nanoparticles in the polymer matrix.     

Preparation and Thermal Degradation of White Fluorinated Polyimide/TiO2 Composite Films with Strong Shielding Performance

A series of white fluorinated polyimide/TiO₂ composite films were prepared by a solution mixing method. They showed high tensile strength beyond 95.1MPa and excellent insulting property with surface and volume resistances exceeding 1.9 × 10¹¹Ω and 2.3 × 10¹² Ω cm, respectively, coupled with water absorptions below 1.1%, water contact angles up to 95.9 and whiteness beyond 58.5. It was found that their optical transparency decreased dramatically with the increasing doping of TiO₂. The thermal degradation of pure fluorinated polyimide (FPI) and representative polyimide/TiO₂ composite film with 5 wt% of TiO₂ (PI/TiO₂-5 wt%) was also studied.     

Microstructural and Optoelectronic Studies on Polyaniline: TiO2 Nanocomposites

Thin films of polyaniline (PANi) and PANi: titanium oxide (TiO₂) composites have been synthesized by sol–gel spin coating technique. The TiO₂ powder of particle size 50–60 nm was synthesized by the sol–gel technique and the polyaniline was synthesized by the chemical oxidative polymerization of aniline. The composite films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, UV-vis spectroscopy and the four-probe method. The results were compared with corresponding data on pure polyaniline films. The intensity of diffraction peaks for PANi:TiO₂ composites is lower than that for TiO₂. The characteristic FTIR peaks of pure PANi are observed to shift to a higher wavenumber in PANi:TiO₂ composite, which is attributed to the interaction of TiO₂ particles with PANi molecular chains. The resistivity measurement shows that the molecular chain constitution of polyaniline is the most important carrier in the polyaniline: nano-TiO₂ composite.     

Degradation of chlorophenol by photocatalysts with various transition metals

In this research, the photocatalytic degradation of 4-chlorophenol (4-CP) in TiO₂ aqueous suspension was studied. TiO₂ photocatalysts were prepared by sol-gel method. The dominant anatase-structure on TiO₂ particles was observed after calcining the TiO₂ gel at 500 °C for 1 hr. Photocatalysts with various transition metals (Fe, Cu, Nd, Pd and Pt) loading were tested to evaluate the effect of transition metal impurities on photodegradation. The photocatalytic degradation in most cases follows first-order kinetics. The maximum photodegradation efficiency was obtained with TiO₂ dosage of 0.4 g/L, retention time of 1 min and air flow rate of 2,500 cc/min. The photodegradation efficiency with Pt-TiO₂ or Pd-TiO₂ is higher than pure TiO₂ powder. The optimal content value of Pt and Pd is 2 wt%. However, the photodegradation efficiency with Fe(1.0 wt%)-TiO₂ and Cu(1.0 wt%)-TiO₂ is lower than pure TiO₂ powder. This paper was prepared at the 2004 Korea/Japan/Taiwan Chemical Engineering Conference held at Busan, Korea between November 3 and 4, 2004.     

Construction of Au/TiO2 Heterojunction with high photocatalytic performances under UVA illumination

Anatase TiO₂ nanoparticles (NPs) were successfully prepared through a hydrothermal approach, and Au NPs at various Au (0.1–2 wt%) contents were photodeposited onto the TiO₂ NPs surface. The photocatalytic efficiency for the Au/TiO₂ NPs for resorcinol photodegradation throughout UVA illumination was assessed. The TEM images and XPS findings indicated that the Au NPs are highly distributed onto TiO₂ surface in the metallic state. The 0.1%Au/TiO₂ NPs exhibited the highest photocatalytic efficiency of about 95.34%; however, 72.36% is given by pure TiO₂ NPs. It was found that the photodegradation rate of 0.1% Au/TiO₂ NPs exhibited 1.5 times of magnitude higher than pure TiO₂ NPs. 0.1%Au/TiO₂ NPs was considered to be the outstanding photoactive due to the ultimate efficient charge-carriers separation through charge transfer between Au and TiO₂ NPs. The Au NPs sizes, its dispersity on TiO₂ surface and surface plasmon resonance (SPR) were believed the critical factors for the higher photocatalytic performance of 0.1% Au/TiO₂ NPs. The prepared photocatalysts are found to be the promising materials for toxic organic compounds remediation and solar conversion.