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.     

Preparation of transparent PVA/TiO2 nanocomposite films with enhanced visible-light photocatalytic activity

Polymer/semiconductor oxide nanocomposite films have been intensively investigated for various applications. In this work, we reported a simple hydrothermal method to fabricate highly transparent poly(vinyl alcohol)/titanium dioxide (PVA/TiO₂) nanocomposite films with enhanced visible-light photocatalytic activity. The as-prepared PVA/TiO₂ nanocomposite films showed high optical transparency in the visible region even at a high TiO₂ content (up to 40 wt.%). The determination of photocatalytic activity by photodegradation of methyl orange (MO) and colorless phenol showed that PVA/TiO₂ nanocomposite films exhibited enhanced visible-light photocatalytic activity and excellent recycle stability. This work provided new insights into fabrication of polymer/TiO₂ nanocomposites as high performance photocatalysts in waste water treatment.     

Dynamic mechanical analysis and broadband electromagnetic interference shielding characteristics of poly (vinyl alcohol)-poly (4-styrenesulfonic acid)-titanium dioxide nanoparticles based tertiary nanocomposites

ABSTRACT

Novel tertiary nanocomposite films comprising of poly (vinyl alcohol) (PVA), poly (4-styrenesulfonic acid) (PSSA) and titanium dioxide (TiO₂) nanoparticles (NP_S) were prepared using simple solvent casting method. The structural, thermal, morphological, thermo-mechanical and electromagnetic interference (EMI) shielding properties of PVA/PSSA/TiO₂ nanocomposite films were investigated. The EMI shielding effectiveness (SE) of PVA/PSSA/TiO₂ nanocomposite films in the X and Ku band was found to be 12 dB and 13 dB respectively at 25 wt% TiO₂ NPs loading. These results demonstrate the possible applications of PVA/PSSA/TiO₂ nanocomposite films as low cost, lightweight and flexible material for EMI shielding.     

Electrochemical synthesis and in situ spectroelectrochemistry of conducting polymer nanocomposites. I. polyaniline/TiO2, polyaniline/ZnO,and polyaniline/TiO2+ZnO

The polyaniline (PAn), polyaniline/titanium dioxide (PAn/TiO₂), polyaniline/zinc oxide (PAn/ZnO), and a novel conducting polymer nanocomposites, polyaniline/titanium dioxide + zinc oxide (PAn/TiO₂+ZnO), were synthesized by in situ electropolymerization and potential cycling on gold electrode. The PAn and nanocomposite films were characterized by cyclic voltammetry, Fourier transform infra‐red (FTIR) spectroscopy, in situ resistivity measurements, in situ UV–Visible, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The differences between cathodic and anodic peaks of three redox couples were obtained for PAn and polymeric nanocomposite films. During cathodic and anodic scans, the shift of potential was observed for polymer nanocomposite films. The characteristic FTIR peaks of PAn were found to shift to lower wavelengthsin polymer nanocomposite films. These observed effects have been attributed to interaction of TiO₂, ZnO, and TiO₂+ZnO particles with PAn molecular chains. Significant differences from in situ resistivity of PAn and nanocomposite films were obtained. The resistance of PAn/TiO₂, PAn/ZnO, and PAn/TiO₂+ZnO films were found to be smaller than the PAn film. The in situ UV–Visible spectra for Pan and polymer nanocomposite films were studied. The results show the intermediate spectroscopic properties between PAn and polymer nanocomposite films. The morphological analyses of PAn and nanocomposite films have been investigated. The nanocomposites SEM and TEM micrographs suggest that the inorganic semiconductor particles were incorporated in organic conducting polymer, which consequently modifies the morphology of the films significantly. POLYM. COMPOS., 35:351–363, 2014. © 2013 Society of Plastics Engineers     

Synthesis and structural characterization of novel bionanocomposite poly(ester-imide)s containing TiO2 nanoparticles, S-valine, and l-tyrosine amino acids moieties

The incorporation of different percents of titanium dioxide (TiO₂) nanoparticles into optically active poly(ester-imide) (PEI), afforded an opportunity to prepare several novel PEI/TiO₂ bionanocomposites (BNC)s. To this point, firstly PEI was synthesized via direct polyesterification of chiral diacid monomer and an optically active phenolic diol using tosyl chloride/pyridine/N,N-dimethylformamide system as a condensing agent. Novel BNC polymers containing TiO₂ nanoparticles were synthesized through ultrasonic irradiation method. With the aim of γ-amidopropyl-triethoxylsilicane as a coupling agent, the surface of nanoscale TiO₂ was modified to decrease aggregation of nanoparticles in polymer matrix. The obtained PEI/TiO₂ BNCs were characterized with FT-IR, thermogravimetric analysis (TGA), scanning electron microscopy, X-ray diffraction, and transmission electron microscopy (TEM) techniques. Consequently, TEM image showed that the nanoparticles of smaller than 50 nm in diameter were uniformly dispersed in the polymer matrix. TGA data demonstrated that new synthesized PEI/TiO₂ BNCs are more thermally stable in compare to pure PEI.     

PLA-TiO2 nanocomposites: Thermal,morphological, structural,and humidity sensing properties

In this paper, the effect of TiO₂ ceramic nanoparticles on the thermal stability, morphology, molecular mass, structure and electrical properties of the polylactic acid-Titanium dioxide (PLA-TiO₂) composites, aimed for relative humidity (RH) sensing have been reported. PLA-TiO₂ nanocomposites films were developed through a spin coating process. The developed films were characterized by X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM) and electrochemical impedance spectroscopy analysis (EIS). To investigate the RH-dependent characteristics, the devices were prepared on pre-patterned ITO substrates. The capacitive and resistive response of the nanocomposite films were studied under RH levels ranging from 20–90%. The PLA-TiO₂ nano-sensing films, having modified surface by acetone etching, exhibited superior morphological and electrical performance when compared to PLA-TiO₂ pristine samples.     

Thermal stability of HCl‐doped‐polyaniline and TiO2 nanoparticles‐based nanocomposites

Electrically conductive HCl doped polyaniline (Pani) : titanium dioxide (TiO₂) nanocomposites thin films were prepared by in‐situ oxidative polymerization of aniline in the presence of different amounts of TiO₂ nanoparticles. Later film casting was done using N‐Methyl‐2‐pyrrolidone (NMP) as a solvent. The formation of Pani : TiO₂ nanocomposites were characterized by Fourier Transform Infra‐Red spectroscopy (FTIR), x‐ray diffraction (XRD) and thermogravimetric analysis (TGA). The stability of the nanocomposites in terms of direct‐current electrical conductivity retention was studied in air by isothermal and cyclic techniques. The films of Pani : TiO₂ nanocomposites were observed thermally more stable under ambient environmental conditions than pure polyaniline film. The stability was seen to be highly dependent on the content of TiO₂ nanoparticles in the nanocomposite films. Due to their high stability, such type of nanocomposites can find place as a replacement material for pure polyaniline in electrical and electronic devices. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Production and characterization of nanocomposites based on poly(amide-imide) containing 4,4′-methylenebis(3-chloro-2,6-diethylaniline) using nano-TiO2 surface-coupled by 3-aminopropyltriethoxysilane

In this work, the poly(amide-imide) (PAI) was synthesized from the polymerization reaction of 4,4′-methylenebis(3-chloro-2,6-diethyl trimellitimidobenzene) as a diacid with 4,4′-methylenebis(3-chloro-2,6-diethylaniline) under green condition using molten tetra-n-butylammonium bromide and triphenylphosphite. Ultrasonic technique was used for preparation of PAI/TiO₂ nanocomposites (PAI/TiO₂ NCs). For the improvement of TiO₂ nanoparticles (NPs) dispersion and enhancing interactions between NPs and polymeric matrix the surface of TiO₂ was successfully modified by silane coupling agent (3-aminopropyltriethoxysilane). The resulting NCs were characterized by FT-IR, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The TGA of the obtained NCs proves the enhancement in the thermal stability with an increase in the percentage of titania NPs. TEM and FE-SEM images showed that the NPs were uniformly dispersed in the polymer matrix. The shielding effect of nano TiO₂ under UV radiation was examined by UV–vis.     

Studies on syntheses and morphology characteristic of chiral novel poly(ester-imide)/TiO2 bionanocomposites derived from l-phenylalanine based diacid

In this study, a new optically active poly(ester-imide) (PEI) was synthesized from the polymerization reaction of N,N′-(pyromellitoyl)-bis-l-phenylalanine diacid with 4,4′-thiobis(2-tert-butyl-5-methylphenol) using tosyl chloride, pyridine and N,N-dimethyl formamide as a condensing agent. The obtained polymer and inorganic metal oxide bionanocomposites composed of poly(ester-imide)/titanium dioxide were synthesized through ultrasonic irradiation. The formation of PEI was confirmed by ¹H NMR, fourier transform IR spectroscopy (FT-IR), specific rotation and elemental analysis. The resulting bionanocomposites were characterized by FT-IR, powder X-ray diffraction (XRD), atomic force microscopy)AFM(, scanning electron microscopy (SEM), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The TEM, SEM and FE-SEM results indicated that the nanoparticles were dispersed homogeneously in PEI matrix on nanoscale. TGA confirmed that the heat stability of the nanocomposite was improved in the presence of TiO₂ nanoparticles.     

Synthesis,structural characterization and properties of novel functional poly(ether imide)/titania nanocomposite thin films

In this study, the synthesis, morphology, and thermal properties of new poly(ether imide)/titania nanohybrid films were investigated. The novel diamine containing functional nitrile groups was prepared in two steps by the nucleophilic substitution reaction and it was fully characterized by different techniques. Reaction of this diamine with pyromellitic dianhydride and 4-aminobenzoic acid gave poly(ether imide) with carboxylic acid end groups. This acid functionalized poly(ether imide) was condense with different amount of TiO₂ nanoparticles to provide organic-inorganic bonding, and the flexible films of these hybrid were prepared. The obtained materials were characterized by Fourier transform-infrared spectroscopy, thermogravimetry analysis (TGA), differential scanning calorimetry, X-ray powder diffraction, UV–Vis spectroscopy, field emission-scanning electron microscopy, and transmission electron microscopy (TEM) techniques. TEM of the nanohybrid films with 12% of TiO₂ contents confirms well dispersion of nanoparticles in the polymer matrix. TGA data indicated that the thermal behavior of the hybrid materials was increased with an increasing the content of TiO₂ nanoparticles. The tensile stress–strain of the hybrids was investigated and the resulting nanocomposites showed good mechanical properties. The permeability and selectivity of the PEI/TiO₂ membranes as a function of the titania weight percentage were study and the results indicated that the permeabilities of CO₂ and N₂ increase with increasing the titania content.     

Reinforcement of structural,thermal and electrical properties and antibacterial activity of PVA/SA blend filled with hybrid nanoparticles (Ag and TiO2 NPs): Nanodielectric for energy storage and food packaging industries‏

In this work, silver nanoparticles (Ag NPs) were prepared using a plant extract which is a cost-effective and environmentally friendly method. The sol-gel method was used to synthesize titanium dioxide nanoparticles (TiO₂ NPs). A solid polymer nanocomposite samples have been prepared via the well-known solution cast way. The present samples were examined using various analytical measurements. The XRD patterns showed a decrease in the degree of crystallinity of the PVA/SA blend due to the addition of the hybrid nanoparticles (Ag and TiO₂ NPs). It was evident by the ATR-FTIR measurement that there is an interaction between the functional groups of the polymeric matrix and the hybrid nanoparticles. XPS confirmed that Ag NPs were loaded onto the surfaces of the PVA/SA/TiO₂ organic-inorganic nanocomposite samples. The TGA curves of the doped samples showed an improvement in their thermal stability compared to the pure sample. From the AC conductivity and electrical modulus, the dynamic ions activity and the kind of relaxation process of the nanocomposites samples were examined. The highest conductivity was log −6.066 S/cm for the polymeric sample doped with 1.60% Ag@TiO₂ NPs, as showed by the AC conductivity measurement. A wide dispersion is observed in the dielectric constant spectra at low frequency. It was also evident from the data that the antibacterial activity of the pristine PVA/SA matrix was growing due to the inclusion of the hybrid nanoparticles to the polymeric matrix. Therefore, the obtained results indicate the applicability of these samples and their potential for use in the semiconductor industry, portable electrochemical batteries and energy storage industry, due to the remarkable improvement in the structural, thermal and electrical properties. Also, the good antibacterial activity of these films provides new samples as effective biomaterials and has the potential to be used in the food packaging industry.     

Characterization and physical properties investigation of conducting polypyrrole/TiO2 nanocomposites prepared through a one‐step “in situ” polymerization method

Nowadays, nanocomposites are a special class of materials having unique physical properties and wide application potential in diverse areas. The present research work describes an efficient method for synthesis of a series of polypyrrole/titanium dioxide (PPy/TiO₂) nanocomposites with different TiO₂ ratios. These nanocomposites were prepared by one‐step in situ deposition oxidative polymerization of pyrrole hydrochloride using ferric chloride (FeCl₃) as an oxidant in the presence of ultra fine grade powder of anatase TiO₂ nanoparticles cooled in an ice bath. The obtained nanocomposites were characterized by Fourier‐transform infrared (FTIR), thermogravimetric analysis (TGA), X‐ray diffraction (XRD), and scanning electron microscope (SEM) techniques. The obtained results showed that TiO₂ nanoparticles have been encapsulated by PPy with a strong effect on the morphology of PPy/TiO₂ nanocomposites. Also, the synthesized PPy/TiO₂ nanocomposites had higher thermal stability than that of pure PPy. The investigation of electrical conductivity of nanocomposites by four‐point probe instrument showed that the conductivity of nanocomposite at low TiO₂ content is much higher than of neat PPy, while with the increasing contents of TiO₂, the conductivity decreases. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Hybrid polyaniline–TiO2 nanocomposite Langmuir–Blodgett thin films: Self‐assembly and their characterization

Polyaniline (PANi)–titanium dioxide (TiO₂) nanocomposite materials were prepared by chemical polymerization of aniline doped with TiO₂ nanoparticles. Surface pressure–area (π‐A) isotherms of these nanocomposites show phase transformations in the monolayer during compression process. Multiple isotherms indicate that the monolayer of the nanocomposite material can retain its configuration during compression‐expansion cycles. Langmuir–Blodgett thin films of PANi–TiO₂ nanocomposite were deposited on the quartz and indium tin oxide coated conducting glass substrates. Fourier transfer infrared spectroscopy and UV–visible spectroscopy study indicates the presence of TiO₂ in PANi, whereas X‐ray Diffraction study confirmed the anatase phase of TiO₂ and particle size (～nm) of PANi–TiO₂. The morphology of Langmuir–Blodgett films of these nanocomposites was also characterized by atomic force microscopy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41386.     

Synthesis and characterization of novel type poly (4-chloromethyl styrene-grft-4-vinylpyridine)/TiO2 nanocomposite via nitroxide-mediated radical polymerization

This paper describes the synthesis and characterization of novel type poly (4-chloromethyl styrene-graft-4-vinylpyridine)/TiO₂ nanocomposite. Firstly, poly (4-chloromethyl styrene)/TiO₂ nanocomposite was synthesized by in situ free radical polymerizing of 4-chloromethyl styrene monomers in the presence of 3-(trimethoxysilyl) propylmethacrylate (MPS) modified nano-TiO₂. Thereafter, 1-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO-OH) was synthesized by the reduction of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO). This functional nitroxyl compound was covalently attached to the poly (4-chloromethyl styrene)/TiO₂ with replacement of chlorine atoms in the poly (4-chloromethyl styrene) chains. The controlled graft copolymerization of 4-vinylpyridine was initiated by poly (4-chloromethyl styrene)/TiO₂ nanocomposite carrying TEMPO groups as a macroinitiators. The coupling of TEMPO with poly (4-chloromethyl styrene)/TiO₂ was verified using ¹H nuclear magnetic resonance (NMR) spectroscopy. The obtained nanocomposites were studied using transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) spectra, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and the optical properties of the nanocomposites were studied using ultraviolet-visible (UV-Vis) spectroscopy.     

Synthesis of CaCO3–P(MMA–BA) nanocomposite and its application in water based alkyd emulsion coating

As part of broader effort to synthesize a new class of water-based composite, hybrid emulsion polymerization was carried out with acrylic monomers [methyl methacrylate (MMA), n-butyl acrylate (BA)]. Nanocomposite of P(MMA–BA)/nano CaCO₃ was synthesized by in situ emulsion polymerization. Water-based alkyd coating with various proportions nano CaCO₃, P(MMA–BA) and its nanocomposite was formulated. Extent of polymerization with and without nano CaCO₃ was measured using gravimetric method. Thermal properties of neat polymer, nanocomposite and coating films were evaluated by TGA and DSC, DTA analysis. Uniform dispersion of nano CaCO₃ in polymer matrix was ensured from SEM/TEM images. Incorporation of nanoparticles to hybrid polymer and nanocomposite to alkyd emulsion showed significant enhancement in mechanical and thermal properties. Dual role of nanocomposite in coating; as a partial binder and a filler to improve property profile of neat coating has been reported.     

Multifunctionality of poly(vinyl alcohol) nanofiber webs containing titanium dioxide

We prepared titanium dioxide/PVA nanocomposite fiber webs for application in multifunctional textiles by electrospinning. The morphological properties of the TiO₂/PVA nanocomposite fibers were characterized using scanning electron microscopy and transmission electron microscopy. Layered fabric systems with electrospun TiO₂ nanocomposite fiber webs were developed using various concentrations of TiO₂ and a range of web area densities, and then the UV‐protective properties, antibacterial functions, formaldehyde decomposition ability, and ammonia deodorization efficiency of the fabric systems were assessed. Layered fabric systems with TiO₂ nanocomposite fiber webs containing 2 wt% TiO₂ nanoparticles at 3.0 g m^?2 web area density exhibited an ultraviolet protection factor of greater than 50, indicating excellent UV protection. The same system showed a 99.3% reduction in Staphylococcus aureus. Layered fabric systems with TiO₂ nanocomposite fiber webs containing 3 wt % TiO₂ nanoparticles at 3.0 g m^?2 web area density exhibited a 85.3% reduction in Klebsiella pneumoniae. Titanium dioxide nanocomposite fiber webs containing 3 wt % TiO₂ nanoparticles at 3.0 g m^?2 web area density exhibited a formaldehyde decomposition efficiency of 40% after 2 h, 60% after 4 h, and 80% after 15 h under UV irradiation. The same system showed an ammonia deodorization efficiency of 32.2% under UV irradiation for 2 h. These results demonstrate that TiO₂ nanocomposite fibers can be used to produce advanced textile materials with multifunctional properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of Functionalized TiO2 on Mechanical,Thermal and Swelling Properties of Chitosan-Based Nanocomposite Films

In this work, a novel type of biodegradable hybrids consisting of titanium dioxide (TiO₂) and chitosan has been fabricated. At first, the TiO₂ nanoparticles were modified with N-trimellitylimido-S-valine diacid to express biomateral moieties through available amino acid groups. The microscopy results demonstrated that the modified TiO₂ nanoparticles were dispersed homogeneously in the chitosan matrix at the nanometric scale, which could be assigned to covalent bonds as well as hydrogen bonding formed between chitosan and TiO₂-diacid. Among all of the prepared films, a nanocomposite film containing 15 wt.% TiO₂ exhibited the highest thermal and mechanical performance.     

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.     

Synthesis and characterization of PVA/PES thin film composite nanofiltration membrane modified with TiO2 nanoparticles for better performance and surface properties

Novel polyethersulfone (PES)/poly (vinyl alcohol) (PVA)/titanium dioxide (TiO₂) composite nanofiltration membranes were prepared by dip-coating of PES membrane in PVA and TiO₂ nanoparticles aqueous solution. Glutaraldehyde (GA) was used as a cross-linker for the composite polymer membrane in order to enhance the chemical, thermal as well as mechanical stabilities. TiO₂ nanoparticles with different concentrations (0, 0.05, 0.1, 0.5 wt.%) were coated on the surface of PVA/PES composite membrane. The morphological study was investigated by atomic force microscopy (AFM), scanning surface microscopy (SEM) and along with X-ray diffraction (XRD). In addition, the membranes performances, in terms of permeate flux, ion rejection and swelling factor were also investigated. It was found that the increase in TiO₂ solution concentration can highly affect the surface morphology and filtration performance of coated membranes. The contact angle measurement and XRD studies indicated that the TiO₂ nanoparticles successfully were coated on the surface of PVA/PES composite membranes. However, rougher surface was obtained for membranes by TiO₂ coating. The filtration performance data showed that the 0.1 wt.% TiO₂-modified membrane presents higher performance in terms of flux and NaCl salt rejection. Finally, TiO₂ modified membranes demonstrated the lower degree of swelling.