Encapsulation of titanium dioxide in styrene/n‐butyl acrylate copolymer by miniemulsion polymerization

Miniemulsion copolymerization of styrene/n‐butyl acrylate was investigated as a means of encapsulating hydrophilic titanium dioxide (TiO₂) in a film‐forming polymer. Dispersion studies of the TiO₂ were first carried out to determine the choice of stabilizer, its concentration, and the dispersion process conditions for obtaining stable TiO₂ particles with minimum particle size. Through screening studies of various functional stabilizers and shelf‐life stability studies at both room and polymerization temperatures, Solsperse 32,000 was selected to give relatively small and stable TiO₂ particles at 1 wt % stabilizer and with 20–25 min sonification. The subsequent encapsulation of the dispersed TiO₂ particles in styrene/n‐butyl acrylate copolymer (St/BA) via miniemulsion polymerization was carried out and compared with a control study using styrene monomer alone. The lattices resulting from the miniemulsion encapsulation polymerizations were characterized in terms of the encapsulation efficiencies (via density gradient column separations; DGC) and particle size (via dynamic light scattering). Encapsulation efficiencies revealed that complete encapsulation of all of the TiO₂ by all of the polymer was not achieved. The maximum encapsulation efficiencies were 79.1% TiO₂ inside 61.7% polystyrene and 63.6% TiO₂ inside 38.5% St/BA copolymer. As the density of the particles collected from the DGC increased from one layer to another, both the average particle size and the number of the TiO₂ particles contained in each latex particle increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3479–3486, 2006     

Influence of anionic and non-ionic surfactants on the synthesis of core-shell Fe3O4@TiO2 nanocomposite synthesized by hydrothermal method

Magnetite spinel nanoparticles (Fe₃O₄) coated titanium dioxide has been prepared by the solvo-hydrothermal method for application in dye degradation and wastewater remediation. The core-shell Fe3O4@TiO2 nanoparticles have been synthesized using titanium butoxide (TBT) and ferric chloride as precursors. In this method, firstly, magnetite nanoparticles have been prepared through a solvothermal process using ethylene glycol as a solvent. Then, titanium butoxide was used as a precursor to synthesize Fe₃O₄@TiO₂ core-shell nanoparticles using the hydrothermal method. The surfactants that were added, in separate synthetic processes, were anionic oleic acid and Sodium Dodecyl sulfonate, and non-ionic Polyvinylpyrrolidone and Polyethylene glycol. The effects of the various surfactants on the fabrication of core-shell magnetic nanoparticles were studied. Various characterization methods have been established to examine the morphology and magnetization features of the nanostructured particles, such as XRD, FTIR, TEM, FESEM, UV-spectroscopy, and VSM, etc., which validated the formation of Titania coated magnetite nanoparticles. The TiO₂ shell formation drastically reduces the saturation magnetization of the magnetic nanoparticles. The Oleic acid as a surfactant produces the smallest nanoparticles. The PVP coating is best amongst these surfactants for the retention of saturation magnetization upon coating.     

Titania-Coated Magnetite and Ni-Ferrite Nanocomposite-Based RADAR Absorbing Materials for Camouflaging Application

A novel core–shell-structured nanocomposite material based on titanium dioxide-coated magnetite and Ni-ferrite has been prepared for RADAR absorbing application in a X-band region. The coating of magnetic particles with TiO₂ was carried out by in situ hydrolysis of titanium tetrabutoxide, and the composite absorber sheets were prepared with epoxy resin. The morphological characterization of the magnetic particles was studied with field emission scanning electron microscope, transmission electron microscope, X-ray diffraction, and vibrating sample magnetometer analysis techniques. The measurement results confirmed the coating of magnetic particles with TiO₂ and reduction of the magnetization of magnetite and Ni-ferrite nanoparticles compared with the uncoated ferrite nanoparticles. Distribution of particle inside the matrix was studied with scanning electron microscope. Microwave absorption study in X-band (8–12 GHz) region was carried out with vector network analyzer. Results showed reflection loss values of ?26.5 db at 9.08 GHz for the magnetite coated with titanium dioxide/conducting carbon black containing sample which increased to ?45.7 db at 9.13 GHz for the Ni-ferrite coated with TiO₂/conducting carbon black formulation. It was observed that coating of magnetic particles resulted in the improvement in the microwave absorption.     

Encapsulation of TiO2 by emulsion polymerization with methyl metacrylate (MMA)

Summary This paper presents a methodology of encapsulation of TiO₂ (Titanium dioxide) by emulsion polymerization on the proposal to modify the physical-chemical properties of the pigment surface. In the proposed methodology the TiO₂ was previously modified by isopropoxy-titanium-tri-isostearate, before being encapsulated by emulsion polymerization using Methyl Methacrylate as monomer. The effects of the polymerization process, type of initiator and monomer concentration in the efficiency of encapsulation were studied. The encapsulated pigment was characterized by Thermogravimetric Analysis (TGA), Light Scattering (LS) and Transmission Electron Microscopy (TEM).     

Synthesis and characterization of polypyrrole dodecylbenzenesulfonate‐titanium dioxide nanocomposites

Nanocomposites of polypyrrole dodecylbenzenesulfonate‐titanium dioxide have been prepared from a colloidal solution of titanium dioxide (TiO₂) nanoparticles. The DC conductivity of samples with different concentrations of TiO₂ has been investigated under dark and light. The doping effect of TiO₂ has been characterized and evaluated by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy, and X‐ray diffraction. TEM shows that TiO₂ nanoparticles have strong effects on the morphology of composites, and conductivity measurements show that the conductivity first increases and then decreases as the percentage of TiO₂ is increased in the composites exhibiting a maximum in conductivity at about 20 wt % of TiO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Characterization of stabilized porous magnetite core–shell nanogel composites based on crosslinked acrylamide/sodium acrylate copolymers

Stabilized and dispersed superparamagnetic porous nanogels based on sodium acrylate (AA‐Na) and acrylamide (AM) in a surfactant‐free aqueous system were synthesized via solution polymerization at room temperature. The formation of magnetite nanoparticles was confirmed and their properties characterized using Fourier transform infrared spectroscopy. Extensive characterization of the magnetic polymer particles using transmission electron microscopy (TEM), dynamic light scattering and zeta potential measurements revealed that Fe₃O₄ nanoparticles were incorporated into the shells of poly(AM/AA‐Na). The average particle size was 5–8 nm as determined from TEM. AM/AA‐Na nanoparticles with a diameter of about 11 nm were effectively assembled onto the negatively charged surface of the as‐synthesized Fe₃O₄ nanoparticles via electrostatic interaction. Crosslinked magnetite nanocomposites were prepared by in situ development of surface‐modified magnetite nanoparticles in an AM/AA‐Na hydrogel. Scanning electron microscopy was used to study the surface morphology of the prepared composites. The morphology, phase composition and crystallinity of the prepared nanocomposites were characterized. Atomic force microscopy and argon adsorption–desorption measurements of Fe₃O₄.AM/AA indicated that the architecture of the polymer network can be a hollow porous sphere or a solid phase, depending on the AA‐Na content. © 2013 Society of Chemical Industry     

Immobilization of TiO2 nanoparticles on montmorillonite clay and its effect on the morphology of natural rubber nanocomposites

Natural rubber/organoclay/titanium dioxide nanocomposites were obtained via mechanical blending using rubber latex, organically modified montmorillonite clay (cloisite 30B) and titanium dioxide (TiO₂). Glycerol was utilized as a dispersant for the inorganic components. Scanning electron microscopy analysis shows that TiO₂ nanoparticles were deposited on the clay surface and that the clay–TiO₂ combination was homogeneously dispersed on the natural rubber. The high aspect ratio and the polar character of the clay layers allowed interactions with individual nanoparticles of TiO₂. The X-ray diffraction patterns reveal an increment of the crystalline character of the NR/C30B/TiO₂ nanocomposites as a consequence of the nanoscale dispersion of the TiO₂ particles. Infrared Spectroscopy spectra indicate compatibility between natural rubber and glycerol due to the formation of hydrogen bonds. A mechanism in particle–natural rubber compatibility, in which glycerol is involved, is proposed. However, nanoscale dispersion was largely dependent on the clay–TiO₂ interactions. This work proposes an easy method to immobilize TiO₂ nanoparticles on clay layers, which allows their dispersion in polymers. Nanocomposites obtained by this method can be used for supports of photocatalyst molecules.     

Chemical modification of TiO2 nanoparticles as an effective way for encapsulation in polyacrylic shell via emulsion polymerization

Encapsulation of inorganic nanoparticles by polymers is one of the interesting research topics that lead to the synthesis of nanocomposites. These nanocomposite materials comprise the properties of both organic polymer and inorganic nanoparticles. Here, hybrid latex particles with core–shell nanostructure were prepared via semi-batch emulsion polymerization. Copolymers of (methyl methacrylate-butyl acrylate) and (dimethylaminoethyl methacrylate-butyl acrylate-acrylic acid) were formed as the inner and outer layers, respectively on the surface of modified TiO₂ nanoparticles as the core. In order to create compatibility between inorganic and polymeric phases, modification of TiO₂ nanoparticles was performed with glycidyl methacrylate with an optimized procedure for the first time and then emulsion polymerization was carried out. The products of each step were fully characterized. The results of dynamic light scattering, TEM and SEM analyses proved the formation of encapsulated hybrid latex particles. DLS and SEM data revealed that the sizes of nanocomposite particles vary between 85 and 120 nm for 0–5 wt% of the modified TiO₂ nanoparticles. Physico-mechanical properties of the obtained nanocomposite films were studied by DMTA. It was found that using only 3 wt% of modified TiO₂ improved those properties of resulting films remarkably.     

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.     

Photocatalytic degradation of methyl orange using polythiophene/titanium dioxide composites

Polythiophene/titanium dioxide (PT/TiO₂) composites were prepared via in situ chemical oxidative polymerization, and the obtained composites were characterized by X-ray photoelectron spectroscopy (XPS), ultraviolet–visible (UV–Vis) diffuse reflectance spectroscopy (DRS) and transmission electron microscopy (TEM). Using methyl orange (MeO) as a target pollutant, the adsorption capacities and the photocatalytic activities of the resulting composites were investigated. The results indicate that PT/TiO₂ composites have good adsorption capacities due to the electrostatic attraction between the positively charged composite particles’ surfaces and MeO; the incorporation of PT into the composites enhances the photocatalytic degradation activity for MeO under both UV and visible light.     

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.     

Gold deposition on Fe3O4/(co)Poly(N‐octadecyl methacrylate) hybrid particles to obtain nanocomposites With ternary intrinsic features

Here, nanocomposite particles with three domains including magnetite nanoparticles, poly(N‐octadecyl methacrylate) (PODMA) or poly(N‐octadecyl methacrylate‐co‐1‐vinylimidazole) (P(ODMA‐co‐VIMZ)), and gold nanoparticles were prepared. Fe₃O₄ nanoparticles with narrow particle size distribution were prepared through a synthetic route in an organic phase in order to achieve good control of the size and size distribution and prevent their aggregation during their preparation. These magnetite nanoparticles, ～ 5 nm in size, were then encapsulated and well‐dispersed in PODMA and P(ODMA‐co‐VIMZ) matrices via a miniemulsion polymerization process to obtain the corresponding nanocomposite particles. The results revealed that Fe₃O₄ nanoparticles were encapsulated and did not migrate towards the monomer/water interface during polymerization. The resulting latex was used as a precursor for the adsorption of Au³⁺ ions on the surface of the polymeric particles and subsequent reduction to produce Fe₃O₄/P(ODMA‐co‐VIMZ)/Au nanocomposite particles. The morphology of the particles from each step was fully characterized by TEM and AFM, and the results of DLS analysis showed their size and size distribution. Measurement of magnetic properties illustrated the superparamagnetic characteristic of the products and it was observed that the encapsulation process and deposition of gold had no effect on the magnetic properties of the resulting particles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

Homogeneously distributed magnetite in the polystyrene spherical particles using the miniemulsion polymerization

The polystyrene spherical particles with homogeneously distributed magnetites were prepared using the conventional miniemulsion polymerization. In the first, the magnetite nanoparticles were coated with oleic acid in aqueous Fe³⁺/Fe²⁺ solution using excess ammonium hydroxide via co-precipitation method. In the second, the miniemulsion polymerization of styrene was carried out using various concentrations of potassium persulfate (KPS) as an initiator, H-08E as an emulsifier, hexadecane as a co-emulsifier and acrylic acid as a dispersing agent in the presence of oleic acid coated magnetite at 70 °C for 24 h. The particle size and its distribution of the homogeneously embedded magnetites were influenced by the concentration of the initiator (KPS) and acrylic acid (AAc). In addition, the emulsifier, H-08E, affects the size and the shape of the PS particles. The optimum conditions for the homogeneously distributed magnetite in the spherical PS particles with the narrow distribution were 5 wt.% styrene, 0.2 g KPS, 0.2 g AAc, and 0.12 g H-08E by inducing 364 nm in diameter, 12.04% in the coefficient of variation (C_v) and 22.1% of the maximum magnetite content.     

Study of polystyrene/titanium dioxide nanocomposites via melt compounding for optical applications

This article presents the study of melt compounding of polystyrene (PS) with various types of titanium dioxide (TiO₂) nanoparticles and surfactants, using a corotating twin screw extruder with multiple screw element configurations. It was found that a properly designed high shear screw configuration and the copolymer of silicone, ethylene oxide, and propylene oxide‐based surfactant produced the greatest degree of nanoparticle dispersion in PS/TiO₂ nanocomposites, whereas a silane‐based surfactant and silicon dioxide (SiO₂) or aluminum oxide (Al₂O₃) coated TiO₂ nanoparticles yielded nanocomposites with the least photocatalytic degradation effects and the best retention of tensile and impact properties. POLYM. COMPOS., 28:241–250, 2007. © 2007 Society of Plastic Engineers     

Preparation of conducting polyaniline/TiO2 composite submicron-rods by the γ-radiolysis oxidative polymerization method

Conducting polyaniline (PAni)–titanium dioxide (TiO₂) composite micron-sized rods have been synthesized using an in situ gamma radiation-induced chemical polymerization method. Aqueous mixtures of aniline, a free-radical oxidant and/or titania nanoparticles were irradiated with γ-rays. The formation of PAni–TiO₂ composite submicron-rods is the result of free aniline cation-radicals and adsorbed aniline cation-radicals on the surface of TiO₂ nanoparticles growing together with the aid of high-energy gamma irradiation. SEM and TEM images represent the PAni–TiO₂ composite rods as having a diameter range of 0.2–0.5 μm. Electrical conductivities were checked by the standard four-point probes method and found to be 0.28 S/cm for bulk PAni and 0.15 S/cm for PAni–TiO₂ composite submicron-rods. UV–visible absorption spectroscopy showed two electronic bands at about 320 and 596 nm for bulk PAni and blue-shifted bands due to the formation of PAni–TiO₂ composites. Thermogravimetric analysis revealed that the composites have a higher degradation temperature than polyaniline alone.     

Comparison of microstructure,toughness, mechanical properties and work hardening of titanium/TiO2 and titanium/SiC composites manufactured by accumulative roll bonding (ARB) process

In this study, the effects of TiO₂ ceramic nanoparticles and SiC microparticles on the microstructure, mechanical properties and toughness of titanium/TiO₂ nanocomposite and titanium/SiC composite were investigated. To achieve this goal, TiO₂ and SiC ceramic particles were incorporated as the reinforcement in titanium through the ARB (accumulative roll bonding) process. By adding SiC ceramic particles, the mechanical properties of the composite and the nanocomposite were enhanced, while their toughness was decreased, as compared to TiO₂ nanoparticles. After applying 8 cycles of the ARB process, UTS in Ti/5 vol% SiC composite reached to about 1200 (MPa), as compared to that in Ti/0.5 wt% TiO₂ nanocomposite, which was about 1100 (MPa). Furthermore, toughness in the Ti/5 vol% SiC composite and the Ti/0.5 wt% TiO₂ nanocomposite was 60 and 29 J/m³, respectively. Finally, SEM and TEM images showed SiC microparticles clustering in Ti/SiC composite samples and a suitable distribution of TiO₂ nanoparticles in the Ti/TiO₂ nanocomposite. By adding TiO₂ nanoparticles, mechanical properties and work hardening coefficient were found to be increased, as compared to those of the monolithic samples. TiO₂ nanoparticles, after being distributed in the titanium matrix through the ARB process, caused pin dislocations. As clearly shown in TEM images, dislocation tangles around TiO₂ nanoparticles acted as the main mechanism improving the work hardening coefficient.     

Synthesis of conducting polyaniline/TiO2 composite nanofibres by one‐step in situ polymerization method

Conducting polyaniline (PANI)/titanium dioxide (TiO₂) composite nanofibres with an average diameter of 80–100 nm were prepared by one‐step in situ polymerization method in the presence of anatase nano‐TiO₂ particles, and were characterized via Fourier‐transform infrared spectra, UV/vis spectra, wide‐angle X‐ray diffraction, thermogravimetric analysis, and transmission electron microscopy, as well as conductivity and cyclic voltammetry. The formation mechanism of PANI/TiO₂ composite nanofibres was also discussed. This composite contained ～ 65% conducting PANI by mass, with a conductivity of 1.42 S cm^?1 at 25°C, and the conductivity of control PANI was 2.4 S cm^?1 at 25°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and characterization of high-surface-area titanium dioxide by sol-gel process

One of the important ways to improve photocatalytic efficiency is to prepare catalyst with enhanced surface area. In this work, titanium dioxide (TiO₂) nanoparticles having enhanced surface area were synthesized under the interference of SiO₂. The mixed oxide, SiO₂-TiO₂ (10% mol% Si), was prepared by a sol-gel procedure using titanium tetra-n-butoxide as Ti-precursor. The commercial SiO₂ nanoparticles were added into the TiO₂ sols after hydrolysis. After condensation and calcination heat treatment, the SiO₂-TiO₂ nanoparticles were obtained. To achieve the purpose of obtaining the high-surface-area TiO₂, the SiO₂ was removed subsequently by aqueous NaOH solution. The TiO₂ products were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), electron spectroscopy for chemical analysis (ESCA), and by N₂ adsorption-desorption isotherm. A fine mesoporous structure was formed for as-prepared TiO₂ after calcination at 400^°C and the average pore diameter was about 7 nm. The porous TiO₂ products possess mixing phases of anatase and rutile. Phase transformation from anatase to rutile occurred when the samples were calcined. The phase transition temperature is sensitive to the silicon content. The particle size of ～43 nm remained constant upon calcinations from 500 to 700^°C. The specific surface area was increased up to 66% compared to regular TiO₂ samples that were prepared by the similar sol-gel procedure. The porous TiO₂ nanostructures exhibited enhanced photocatalytic performance to decompose methylene blue under UV irradiation.     

The toxicity in vitro of titanium dioxide nanoparticles modified with noble metals on mammalian cells

The aim of the presented work was to evaluate the effect of modification of titanium dioxide nanoparticles with noble metals and their oxides on selected mammalian cells. The in vitro cytotoxicity studies of titanium dioxide (TiO₂) nanoparticles modified with Au, Ag, Pd, Ag₂O, and PdO with reference to the unmodified TiO₂ nanoparticles were presented. The evaluation of cytotoxic activity of the tested nanocomposite particles was carried out using three cell lines: Caco-2 colorectal epithelial adenocarcinoma cells, BJ normal human skin fibroblasts, and L929 mouse fibroblasts. The in vitro studies included determination of cell viability after 24 and 48 hours of exposure to the nanocomposite particles, using the MTT assay, as well as flow cytometry with Annexin V-FITC staining. Our results indicate that irrespectively of the kind of cell line and assay used, nanoparticles of unmodified titanium dioxide as well as those with addition of gold and palladium have a slight impact on cell viability at the investigated concentration range (10-200 μg/mL). Nanoparticles with addition of silver (Ag and Ag₂O), were found to have significantly higher toxic effect, the level of which varied depending on the cell line and assay used.