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.     

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.     

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     

Physical properties of epoxy resin/titanium dioxide nanocomposites

A polymeric nanocomposite system (nanodielectric) was fabricated, and its mechanical properties were determined. The fabricated nanocomposite was composed of low concentrations of monodispersed titanium dioxide (TiO₂) nanoparticles and an epoxy resin specially designed for cryogenic applications. The monodispersed TiO₂ nanoparticles were synthesized in an aqueous solution of titanium chloride and polyethylene glycol and subsequently dispersed in a commercial‐grade epoxy resin (Araldite® 5808). Nanocomposite thin sheets were prepared at several weight fractions of TiO₂. The morphology of the composites, determined by transmission electron microscopy, showed that the nanoparticles aggregated to form particle clusters. The influence of thermal processing and the effect of filler dispersion on the structure–property relationships were identified by differential scanning calorimetry and dynamic mechanical analysis at a broad range of temperatures. The effect of the aggregates on the electrical insulation properties was determined by dielectric breakdown measurements. The optical properties of the nanocomposites and their potential use as filters in the ultraviolet–visible (UV–vis) range were determined by UV–vis spectroscopy. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

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     

The TiO2–Clay-LDPE Nanocomposite Packaging Films: Investigation on the Structure and Physicomechanical Properties

The role of nanoclays and TiO₂ nanoparticle loadings were investigated on low density polyethylene crystalline structure, in addition to studying packaging film properties such as barrier, thermal and mechanical properties. The polymer crystal study indicated for the orthorhombic crystal phase and about 20% lower degree of crystallinity for nanocomposites containing more than 2 wt.% TiO₂ nanoparticles. Based on the X-ray diffraction technique, the dispersion of nanoclays was improved to almost good degree of clay exfoliation with the company of 4 wt.% TiO₂ nanoparticles. In agreement with XRD results, the TEM morphological studies mainly suggest that TiO₂ has a helpful effect on nanoclay exfoliation. The increase in degradation temperature of nanocomposites may be attributed to the formation of inorganic char on polymer melt. The barrier properties of TiO₂/clay nanocomposite packaging films depend mainly on nanoclay loading with an unclear trend from TiO₂ nanoparticles. The increase in elastic modulus and the yield stress of nanocomposite films showed great effects on film mechanical properties by nanoclays.     

Effects of carbon‐coated titanium dioxide nanoparticles as a photostabilizer on the photodegradation of rigid poly(vinyl chloride)

In this study, nanocomposites of rigid poly(vinyl chloride) (UPVC) using the synthesized carbon‐coated titanium dioxide (TiO₂) nanoparticles and commercial powder of titanium dioxide (with rutile structure) were prepared by melt blending. The presence of carbon‐coated TiO₂ nanoparticles with rutile structure in UPVC matrix led to an improvement in photo stability of UPVC nanocomposites in comparison with commercial UPVC. The photocatalytic degradation behavior of nanocomposites was investigated by measuring their structural changes, surface tension, and mechanical and morphological properties before and after UV exposure for 700 h. It was found that mechanical and physical properties of UPVC nanocomposites are not considerably reduced after UV exposure in the presence of carbon‐coated TiO₂ nanoparticles even in small percentage of nanoparticles in comparison with the presence of commercial TiO₂ particles. Therefore, it can be concluded that UPVC/TiO₂ nanocomposite with low content of carbon‐coated TiO₂ nanoparticles(0.25 wt %) illustrated high stability under light exposure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40228.     

Morphology and properties of highly filled iPP/TiO2 nanocomposites

Nanocomposites based on isotactic polypropylene (iPP) and titanium dioxide (TiO₂) nanoparticle containing 1–15 vol% (4.6–45.5 wt%) of the nanoparticle were prepared by the melt blending process. The effect of an anhydride‐modified polypropylene as a compatibilizer on dispersion of TiO₂ nanoparticles was assessed using SEM. TGA and DSC analysis were performed to study the thermal properties of the nanocomposites. Crystalline structures of iPP in the presence of TiO₂ were analyzed by XRD. Mechanical properties of the nanoparticles were measured and a micromechanical analysis was applied to quantify interface interaction between the polymer and particle. SEM results revealed improvement of TiO₂ particle dispersion by adding the compatibilizer. It was shown that the thermal stability and crystalline structure of the nanocomposite are significantly affected by the state of particle dispersion. TiO₂ nanoparticles were shown to be strong β‐nucleating agents for iPP, especially at concentrations less than 5 vol%. Presence of the β‐structure crystals reduced the elastic modulus and yield strength of the nanocomposites. Micromechanical analysis showed enhanced interaction between organic and inorganic phases of the compatibilized nanocomposites. POLYM. ENG. SCI., 54:874–886, 2014. © 2013 Society of Plastics Engineers     

Ultrasound Synthesis of Polyindole–TiO2 Nanocomposite and Evaluation of Antibacterial Activity

The present work reports the synthesis and evaluation of antimicrobial activity of polyindole–TiO₂ nanocomposite. Polyindole–TiO₂ nanocomposite was synthesized by aqueous in situ chemical polymerization of indole using ammonium persulfate as an oxidant under ultrasonic condition. The synthesized polyindole and polyindole–TiO₂ nanocomposites were characterized by ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscope, thermogravimetric analysis, and X-ray diffraction techniques. A sharp peak at ～1,402?cm^?1 is due to the stretching vibrations of O?Ti?O bond in polyindole–TiO₂ nanocomposite. The X-ray diffraction pattern shows the major diffraction peaks at 25°C and 48°C, indicating TiO₂ in anatase form. Polyindole–TiO₂ shows maximum activity against gram-positive Staphylococcus aureus and Bacillus subtilis as compared to gram-negative Escherichia coli.     

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.     

Effects of particle type on thermal and mechanical properties of polyoxymethylene nanocomposites

The effects of particle size of titanium dioxide (TiO₂) on mechanical, thermal, and morphological properties of pure polyoxymethylene (POM) and POM/TiO₂ nanocomposites were investigated and compared with the results for nanoparticle ZnO in the same matrix, reported in a previous paper. POM/TiO₂ nanocomposites with varying concentration of TiO₂ were prepared by the melt mixing technique in a twin screw extruder, the same method that used for blending the homogeneous ZnO nanocomposites. The dispersion of TiO₂ particles in POM nanocomposites was studied by scanning electron microscopy (SEM). The agglomeration, as observed by the mechanical properties of TiO₂ particles in the polymer matrix, increased with increasing TiO₂ content, a result not found for ZnO even at lower particle sizes. Increasing the filler content of POM/TD32.4 and POM/TD130 (130 nm) nanocomposites resulted in a decrease in tensile strength. The Young modulus, stress at break and impact strength of TiO₂ nanocomposite did not improve with increasing filler contents, in opposition to the better agglomeration conditions of ZnO nanocomposite even at lower particle sizes. Because of agglomeration, the POM/TD32.4 nanocomposites had lower mechanical properties and lower degradation temperature than the POM/TD130 ones. The sizes of nanoparticles determined the agglomeration, but however, the agglomeration also depended on the type of nanoparticles, even when using the same matrix (POM) and the same mixing method. TiO₂ nanoparticles were more difficult to mix and were more agglomerated in the POM matrix as compared to ZnO nanoparticles, regardless of the size of the nanoparticles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of clay–TiO2 nanocomposite thin films with barrier and photocatalytic properties for food packaging application

In this study, low‐density polyethylene (LDPE) nanocomposite films with two types of nanoparticles, TiO₂ (3 wt %) and Closite 20A (3 and 5 wt %), were prepared using a melt blow extrusion as an industrial method and their properties such as mechanical properties, water vapor, oxygen and carbon dioxide gas barrier, and antimicrobial activity were tested. Transmission electron microscopy (TEM) and X‐ray diffraction (XRD) were also performed to determine the degree of dispersion and exfoliation of nanoparticles. Mechanical test indicated that the reinforcement in the presence of the nanocomposites was more than that with their conventional counterparts, and the highest stiffness was achieved in a sample containing 5 wt % clay and 3 wt % TiO₂. Exfoliation of silicate layers and a good dispersion of TiO₂ nanoparticles in LDPE were achieved as confirmed by XRD and TEM. The gas barrier properties were improved after formation of the nanocomposites especially by insertion of 5 wt % of clay nanoparticles as a filler in the LDPE matrix. The photocatalytic effect of the nanocomposite film was carried out by antimicrobial evaluation against Pseudomonas spp. and Rhodotorula mucilaginosa and by ethylene removal test using 8 W ultraviolet (UV) lamps with a constant relative intensity of 1 mW cm^?2. The greatest effects were recorded by combining UVA illumination and active film. It was also proven that the photocatalyst thin film with improved barrier properties prepared by extrusion could be used in horticultural product packaging applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41764.     

Preparation of TiO2/carbon nanotubes photocatalysts: The influence of the method of oxidation of the carbon nanotubes on the photocatalytic activity of the nanocomposites

A method for the preparation of efficient TiO₂/multi-wall carbon nanotubes nanocomposite photocatalysts by precipitation of anatase TiO₂ nanoparticles onto differently oxidized carbon nanotubes is presented. The precursor compound titanium(IV) bromide was hydrolyzed producing pure anatase phase TiO₂ nanoparticles decorated on the surface of the oxidized carbon nanotubes. The oxidative treatment of the carbon nanotubes influenced the type, quantity and distribution of oxygen-containing functional groups, which had a significant influence on the electron transfer properties, i.e., the photocatalytic activity of the synthesized nanocomposites. The results of C.I. Reactive Orange 16 photodegradation in the presence of all the synthesized nanocomposites showed their better photocatalytic activity in comparison to the commercial photocatalyst Degussa P-25.     

The Effect of Surface Modification of TiO2 with Diblock Copolymers on the Properties of Epoxy Nanocomposites

The TiO₂ nanoparticles were modified by diblock copolymers, poly(methyl methacrylate)-b-polystyrene (PMMA-b-PS), via reversible addition-fragmentation chain transfer (RAFT) polymerization, and the epoxy nanocomposites containing different TiO₂ and with different contents were prepared. Subsequently, the effects of TiO₂ content on the mechanical and thermal properties of nanocomposites were investigated. The results indicated that after grafting copolymers onto TiO₂, the dispersion of TiO₂ and interaction with epoxy matrix could be significantly increased, therefore, the mechanical properties of the nanocomposites were improved greatly. When the TiO₂-PMMA-b-PS content was 1 wt%, the impact strength and flexural strength reached their the best, and increased up to 96% and 43%, respectively. Furthermore, the thermal stability of the nanocomposites was also distinctly improved.     

Influence of Rutile and Anatase TiO2 Nanoparticles on Polyethylene Properties

Nanocomposites from polyethylene and TiO₂ with different shape and size were prepared by direct mixing and masterbatch dilution, respectively. The mechanical properties of nanocomposites were determined and discussed in relation to the nanofiller dispersion. Moreover, the morphological aspects of polyethylene with and without nanofiller were revealed by means of SEM and WAXD. A better dispersion of the nanoparticles and increased mechanical properties were observed in the case of the masterbatch method. No important differences in mechanical and morphological characteristics of anatase and rutile containing polyethylene composites were observed, except a higher increase of the elastic modulus in case of anatase-containing composites.     

Thermal properties of PMMA/TiO2 nanocomposites prepared by in-situ bulk polymerization

The surface of anatase TiO₂ nanoparticles, obtained by the controlled hydrolysis of titanium tetrachloride, was modified by 6-palmitate ascorbic acid. The surface modified TiO₂ nanoparticles were dispersed in methyl methacrylate and mixed with a appropriate amount of poly(methyl methacrylate) to obtain a syrup. The nanocomposite sheets were made by bulk polymerization of the syrup in a glass sandwich cell using 2,2′-azobisisobutyronitrile as initiator. The molar masses and molar mass distributions of synthesized poly(methyl methacrylate) samples were determined by gel permeation chromatography. The content of unreacted double bonds in synthesized samples was determined by ¹H NMR spectroscopy. The influence of TiO₂ nanoparticles on the thermal stability of the poly(methyl methacrylate) matrix was investigated using thermogravimetric analysis and differential scanning calorimetry. The synthesized samples of poly(methyl methacrylate) have different molar mass and polydispersity depending on the content of the surface modified TiO₂ nanoparticles. The values of glass transition temperature of so prepared nanocomposite samples were lower than for pure poly(methyl methacrylate), while the glass transition temperature of samples preheated in inert atmosphere was very similar to the glass transition temperature of pure poly(methyl methacrylate). The thermal stability of nanocomposite samples in nitrogen and air was different from thermal stability of pure poly(methyl methacrylate). POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

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.     

Optimized synthesis of novel hydroxyapatite/CuO/TiO2 nanocomposite with high antibacterial activity against oral pathogen Streptococcus mutans

The main issue of using hydroxyapatite (HA) in dentistry is accumulation of microorganisms on it that causes tooth decay. The use of nanoparticles can decrease the accumulation of microorganisms, including Streptococcus mutans on HA, and increase its antibacterial effect. The present study aimed to determine the optimal conditions to synthesize HA/CuO/TiO₂ nanocomposites with the highest antibacterial properties. Utilizing the Taguchi method, nine experiments were designed to fabricate nanocomposites using 3 factors of hydroxyapatite, CuO and TiO₂ nanoparticles. The antibacterial activity of the synthesized nanocomposites was evaluated by the colony forming units (CFU) method against S. mutans. Nanocomposite synthesized under experimental conditions 2 (hydroxyapatite 20 mg/ml, CuO 1.50 mg/ml and TiO₂ 1.60 mg/ml) had the highest effect on reducing the growth of S. mutans (1.24 CFU/ml). The results demonstrated the improvement of structural properties, antibacterial activity, and thermal stability by formation of nanocomposite. Owing to the desirable antibacterial properties of the HA/CuO/TiO₂ nanocomposite, it can be used to improve performance in various dental fields.     

Novel nanocomposite based on poly (xanthoneamide-triazole-ethercalix) and TiO2 nanoparticles: preparation,characterization, and investigation of nanocomposite capability in removal of cationic water pollutants

A new multifunctional nanocomposite based on poly (xanthoneamide-triazole-ethercalix) (PXTE) and TiO₂ nanoparticles (PXTE–TiO₂), which is a novel class of multiphase material containing nanosized inorganic material within polymer matrix, was prepared and characterized fully in this article. At first, PXTE was synthesized through click reaction, and then PXTE–TiO₂ nanocomposite was prepared by chemical immobilization of PXTE onto the modified TiO₂ nanoparticles. Nuclear magnetic resonance, Fourier transform infrared, X-ray diffraction, scanning electron microscopy, differential scanning calorimetry, and thermal gravimetric analysis were applied for characterization of synthesized materials. Dye and ion removal capability of PXTE–TiO₂ nanocomposite were investigated by batch method for methylene blue and cadmium ion. The results showed that thermal stability and potential applicability of PXTE–TiO₂ nanocomposite make it as a good candidate for wastewater refinement.     

In situ polymerized nanocomposites of poly(butylene succinate)/Tio2 nanofibers: molecular weight,morphology, and thermal properties

In this study, the nanocomposites of poly(butylene succinate) (PBS) and TiO₂ nanofibers were first synthesized via in situ polymerization. Molecular weight, morphology, and thermal properties of the nanocomposites were characterized. As the weight percentage of TiO₂ nanofibers increased from 0 to 2%, the molecular weight of PBS in the nanocomposites decreased gradually compared with that of pure PBS. In morphology, the nanocomposites were constituted by free PBS and PBS‐grafted TiO₂ nanofibers (PBS‐g‐TiO₂), which were proved by the Fourier transform infrared, scanning electron microscopy (SEM), and transmission electron microscopy. In addition, the SEM demonstrated the strong interfacial interaction and homogeneous distribution between TiO₂ nanofibers and PBS matrix. The thermal properties determined by differential scanning calorimetry and thermogravimetric analysis included the increasing of cold crystallization temperatures, the melting temperatures, and the thermal stability. Besides, the crystallinity and the rate of crystallization of the nanocomposites were enhanced, which were also observed by the X‐ray diffraction. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013