Influence of a non-polar medium (alkane and molten polypropylene) on the titanium n-butoxide hydrolysis-condensation reactions

Study of hydrolysis-condensation reactions of titanium n-butoxide precursor into an unusual medium and non-classical conditions was carried out. Kinetic data were reached in a temperature range of 130–250°C from FTIR, TGA–GC–MS and rheological techniques. These results were obtained into an alkane dispersing medium, (Squalane: 2,6,10,15,19,23-hexamethyltetracosane), and compared to the ones determined from the hydrolysis-condensation reactions of the titanium dioxide precursor carried in molten polypropylene (PP) during extrusion process. The transposition of these knowledge to the in situ synthesis of titanium dioxide in molten PP matrix by reactive extrusion lead to the formation of a fine dispersion of few nanometer diameter (~5 nm) of TiO₂ particles. Finally, the viscoelastic behaviour of the nanocomposite has been strongly altered in the terminal relaxation zone as permanent secondary plateau (solid-like behavior), attributed to some fractal arrangement of the inorganic domains was observed.     

Morphology and viscoelasticity of PP/TiO2 nanocomposites prepared by in situ sol–gel method

PP/TiO₂ nanocomposites were prepared from an original method based on the hydrolysis‐condensation (sol–gel method) reactions of titanium alkoxide inorganic precursor premixed with polypropylene (PP) under molten conditions. Nanocomposites with a mean diameter of primary particles lower than 5 nm were then prepared. The TiO₂ particle dispersion in the PP matrix was characterized over a wide length scale from the combination of small angle X‐ray scattering, transmission electron microscopy, and linear viscoelasticty of molten nanocomposites. As a result, a fractal structure of these particles was highlighted at the highest concentration (φ_r ≥ 0.014) with a characteristic aggregation size d_aggr ≈ 130 nm. The relationships between fractal structure and linear viscoelastic have been discussed from the main works of the literature on the reinforcement of nanocomposites. The drastic alteration of the terminal relaxation zone (solid‐like behavior) is correlated to the formation of an aggregate‐particle network. The study of the nonlinear viscoelastic behavior (Payne effect) agrees qualitatively with this reinforcement mechanism. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1213–1222, 2010     

Organically Modified Silicates and Ceramics as Two-Phasic Systems: Synthesis and Processing

Based on the concept of controlling the particle size by the surface free energy, the growth of sol-gel derived nanoparticles (Al₂O₃, TiO₂, ZrO₂) has been investigated in presence of molecules with binding ability to the growing particles. The investigations show that the use of silanes, carboxylic acid or β-diketones allows to replace electrostatic sol stabilisation by steric sol stabilisation and through this, high solid content sols can be obtained. The introduction of these sols into orgaic or ormocer type of matrices leads to nano composites with degrees of filling up to 40 wt.-% without agglomeration and with high optical quality. Already developed TiO₂ containing bulk materials, ultrahard coatings on plastic and adhesives for fiber to chip coupling are examples for the usefulness of this alternative sol-gel route. The nanocomposite materials show interesting mechanical and thermomechanical properties such as high hardness or low thermal expansion compared to unfilled systems.     

Synthesis and studies on photochromic properties of vanadium doped TiO2 nanoparticles

Pure and (0.5–3 at%) vanadium doped TiO₂ nanoparticles have been synthesized by wet chemical method. The as synthesized materials have been characterized by using XRD, atomic force microscope (AFM), Raman, EPR and UV–vis spectroscopy techniques. From XRD studies, both pure as well as vanadium doped TiO₂ have been found to show pure anatase phase. The value of lattice constant c is smaller in doped TiO₂ as compared to undoped and has been found to decrease with increase in vanadium concentration. AFM studies show formation of spherical particles with particle size ～23 nm in all the samples. Photochromic behavior of these materials has been studied by making their films in alkyd resin. Vanadium doped TiO₂ films show reversible change in color from beige-yellow to brownish violet on exposure to UV light. The mechanism of coloration and bleaching process has been discussed.     

Tuning the properties of a black TiO2-Ag visible light photocatalyst produced by a rapid one-pot chemical reduction

A highly efficient black TiO₂-Ag photocatalytic nanocomposite, active under both UV and visible light illumination, was synthesized by decorating the surface of 25 nm TiO₂ particles with Ag nanoparticles. The material was obtained via a rapid, one-pot, simple (surfactant and complexing agent free) chemical reduction method using silver nitrate and formaldehyde as a metal salt and reducing agent, respectively. The nanocomposite shows an increase of over 800% in the rate of photocatalytic methylene blue dye degradation, compared to commercial unmodified TiO_2, under UV-VIS illumination. Unlike pure TiO₂, the nanocomposite exhibits visible light activation, with a corresponding drop in optical reflectance from 100% to less than 10%. The photocatalytic properties were shown to be strongly enhanced by post-reduction annealing heat treatments in air, which were observed to decrease, rather than coarsen, silver particle size, and increase particle distribution. This, accompanied by a variation in the silver surface oxidation states, appear to dramatically affect the photocatalytic efficiency under both UV and visible light. This highly active photocatalyst could have wide ranging applications in water and air pollution remediation and solar fuel production.     

Characterization of silicone oil emulsions stabilized by TiO2 suspensions pre-adsorbed SDS

To study the effects of pre-adsorbed emulsifier on Pickering emulsion stability, the preparation of silicone oil emulsions by TiO₂ suspensions pre-adsorbed sodium dodecyl sulfate (SDS) at the fixed TiO₂ concentration of 0.15 g was carried out below a fiftieth of critical micelle concentration (cmc) of SDS, where all added amounts of SDS are adsorbed on the TiO₂ particles. The stability of the Pickering emulsions incorporating TiO₂ suspensions pre-adsorbed SDS was investigated by measuring the volume fraction of emulsified silicone oil, adsorbed amounts of TiO₂ suspensions pre-adsorbed SDS, oil droplet size, and some rheological responses such as the stress-strain sweep curve and strain and frequency dependences of dynamic viscoelastic moduli. The silicone oil was almost emulsified by TiO₂ suspensions pre-adsorbed SDS above cmc/10³. Increasing in the adsorbed amount of SDS on the TiO₂ particles leads to an increase in the adsorbed amounts of TiO₂ suspensions pre-adsorbed SDS. Such silicone oil emulsions for the first time showed two yield stresses in the stress-strain sweep curve as well as the oscillatory stress-strain curve. The respective yield stresses also increase with an increase in the adsorbed amounts of TiO₂ suspensions pre-adsorbed SDS. From such characteristic rheological properties and a partial sedimentation of some TiO₂ particles remained in the dispersion medium, we proposed the formation of a three dimensional network of the flocculated TiO₂ particles pre-adsorbed SDS on the silicone oil droplets.     

Study of Pt/TiO2 nanocomposite for cancer-cell treatment

The increasing incidence of cancer all over the world demands new, effective and secure materials for treatment. In this paper, we propose Pt/TiO₂ nanocomposite for cancer-cell treatment because noble metal nanoparticles are supposed to enhance the photocatalytic activity of TiO₂ nanoparticles. To evaluate the cancer-cell killing effect of our Pt/TiO₂ nanocomposite, TiO₂ and Au/TiO₂ nanoparticles are also introduced. The prepared Pt/TiO₂ nanocomposite are characterized with transmission electron microscopy (TEM) and UV–vis adsorption spectra. Results of cell treatment indicate that Pt/TiO₂ nanocomposite, as extremely stable metal–semiconductor nanomaterial, can exhibit a very high photodynamic efficiency under a mild ultraviolet radiation. And our Pt/TiO₂ nanocomposite shows to be more effective in cancer-cell treatment than TiO₂ and Au/TiO₂ nanoparticles. As a result, Pt/TiO₂ nanocomposite may be supposed to have a promising application for cancer-cell treatment.     

Highly efficient UV–visible absorption of TiO2/Y2O3 nanocomposite prepared by nanosecond pulsed laser ablation technique

Nanostructured TiO₂-based composites are promising materials because of their superior optical, structural, and electronic properties relative to pristine nanostructured TiO₂. The enhanced properties of TiO₂-based composites have been used in several important applications such as gas sensors, solar cells, and photocatalytic applications. In the past, numerous materials have been coupled with TiO₂ to enhance their optical properties. In this work, full-spectrum (UV and Visible) responsive TiO₂ /Y₂O₃ nanocomposite has been synthesized via pulsed laser ablation in liquid (PLA) to study the impact of Y₂O₃ on the structural, morphology, and optical property of the TiO₂. The nanostructured composites prepared were characterized by XRD, Raman spectroscopy, Field-Emission Scanning Electron Microscope (FESEM) attached with Energy-Dispersive X-ray spectroscopy (EDX), Photoluminescence, XPS, and UV–Vis absorbance spectra. The result demonstrates that the coupling Y₂O₃ with TiO₂ not only changes the structural, optical, and morphology of the TiO₂ but also significantly amplified the light absorption characteristics of the TiO₂ within the UV and visible region. The synthesized TiO₂ /Y₂O₃ nanocomposite could potentially be useful for visible-light responsive applications.     

Enhanced photodegradation of 2,4-dinitrophenol by n–p type TiO2/BiOI nanocomposite

Photocatalysis has recently been regarded as one of the most viable technologies for water treatment. Scholars all over the world are focusing on nanocomposites for water treatment for efficient and effective sanitization of bodies of water. Because of their high surface area, high chemical reactivity, excellent mechanical strength, low cost, and nanoscale composite materials have enormous potential to purify water in a various way. In this study, n-type TiO₂ was synthesized and tailored to produce a TiO₂/BiOI n–p nanocatalyst for enhanced photodegradation of 2,4-dinitrophenol (2,4-DNP) under UV-A and solar light respectively. Because of the formation of a heterojunction between BiOI and TiO₂, the photocatalytic activity in TiO₂/BiOI absorbs strongly in both the UV and visible regions and it has a lower recombination rate of the e^-/h⁺ pairs. Furthermore, the generation of OH^?, O₂^?– radicals during the oxidation process is attributed to the photodegradation of 2,4-DNP. The results revealed that the TiO₂/BiOI manifest outperformed BiOI and TiO₂ in terms of photocatalytic function. XRD, BET, HR-SEM-EDX with ECM, HR-TEM, FT-IR, PL, and UV-DRS techniques determined the photocatalyst composition. The HR-SEM images clearly showed that the particles are less than 27 ?nm in size. Thus, nanocomposite materials have played an important role in water purification.     

Effect of synthesis parameters on the particle size, composition and colloid stability of polypyrrole–silica nanocomposite particles

 The effect of varying the oxidant, monomer and silica sol concentrations, silica sol diameter, polymerization temperature, stirring rate and oxidant type, on the particle size, polypyrrole content and conductivity of the resulting polypyrrole– silica colloidal nanocomposites has been studied. Surprisingly, nanocomposite formation appears to be relatively insensitive to most of the above synthesis parameters. One synthesis parameter which does have a significant and reproducible effect is the stirring rate: smaller, more monodisperse nanocomposite particles are obtained from rapidly stirred reaction solutions. However, this effect is only observed for the (NH₄)₂S₂O₈ oxidant. An alternative oxidant, H₂O₂/Fe³⁺, was found to give nanocomposites of similar particle size, polypyrrole content and conductivity to those obtained using the (NH₄)₂S₂O₈ oxidant. The colloid stability of these polypyrrole–silica nanocomposite particles depends on their silica content. The colloid stability of a silica-rich nanocomposite prepared using the (NH₄)₂S₂O₈ oxidant in the presence of electrolyte was comparable to that of a silica sol, whereas a polypyrrole-rich nanocomposite prepared using FeCl₃ had markedly poorer colloid stability under these conditions. These observations are consistent with a charge stabilization mechanism for these nanocomposite particles. Received: 5 March 1998 Accepted: 27 April 1998     

Liquid-phase Reductive Deposition as Novel Preparation Method for Highly Dispersive Nickel Catalysts

We have been developing the selective deposition method onto TiO₂ nanoparticles, named as the liquid-phase selective-deposition method, where TiO₂ plays a role of formation center of Ni nanoparticles as well as protection from the aggregative growth of the particles. The concept of this method is to well disperse and stabilize Ni nanoparticles on TiO₂ surface by specific adsorption of Ni precursory complexes and then heterogeneous nucleation on the adsorption sites. The particle size was decreased with increasing the amount of Zn added, thus the catalytically active Ni surface area was increased. The selective deposition onto TiO₂ surface and addition of Zn to the nanoparticle promoted the catalytic activity of Ni–Zn nanoparticle, e.g. the catalytic activity of Ni–Zn/TiO₂ was ca. 10 times higher than that of the unsupported Ni nanoparticles. Ni in the nanocomposite was assigned as metallic, although their surface was oxidized under the atmospheric condition, but Zn and B were deposited as their oxide.     

Molecular Assembly by Sequential Ionic Adsorption of Nanocrystalline TiO2 and a Conjugated Polymer

Abstract

Cationic nanocrystalline TiO₂ particles have been synthesized for which the size and composition of the nanoparticles were analyzed by a transmission emission microscopy and energy dispersive x‐ray spectrometer (EDXS). Multilayered films have been fabricated by sequential adsorption of TiO₂ nanoparticles and poly(3‐thiophene acetic acid) (PTAA). Each layer of the nanoparticles and PTAA in the thin film has also been characterized by x‐ray photoelectron spectroscopy, atomic force microscopy, and UV‐visible spectroscopy. These types of multilayered nanocomposite films may find applications in the fabrication of efficient light harvesting photovoltaic cells.     

Rheological and antimicrobial properties of epoxy-based hybrid nanocoatings

The modification of nanocomposite coatings with fillers having unique characteristics in the polymeric matrix is a promising strategy to enhance the durability as well as to prevent the growth of microorganisms that decrease the stability of the materials. This study was conducted to evaluate the rheological and antimicrobial behavior of epoxy-based nanocomposite coatings filled with nanosilica, titanium oxide (TiO₂) and zinc oxide (ZnO) against Staphylococcus aureus and Escherichia coli. A rheometer was used for characterizing the rheological properties of the various fillers embedded epoxy nanocomposite coatings. All of the composites inhibited the growth of Staphylococcus aureus and Escherichia coli on modified Kirby Bauer antimicrobial testing, only when they are in contact with samples. Upon quantitative analysis, bioactive constituent dependent antimicrobial activity was observed which increased with the exposure of contact times. The epoxy/silica/TiO₂/ZnO (ESTZ) coating showed the highest bacterial reduction of more than 95% for 4 h of treatment. The bioactivity was decreased for the case of epoxy/silica/ZnO (ESZ) or epoxy/silica/TiO₂ (EST). The combined effect of the nanosilica, TiO₂, and ZnO shows the highest performance in terms of stress, viscosity and torque compared to the individual effect of these three fillers onto the epoxy. Results showed that the shear stress of ESZ, EST, epoxy/silica (ES), and ESTZ coating was increased by 4.4%, 7.7%, 32.2%, and 42%, respectively, compared to the neat epoxy (NE) coating. The torque versus strain curve also showed that the torque of ESTZ composites was the highest (0.52 mN m) compare to NE (0.36 mN m), ESZ (0.38 mN m), EST (0.40 mN m), and ES (0.45 mN m). The studies indicate that the epoxy-based thermoset nanocomposite coatings can be utilized as bactericidal surfaces for the industrial and medical purpose to reduce microbial growth.     

接枝共聚法制备二氧化钛/聚（苯乙烯-二乙烯基苯）复合微球

本文以KH560、苯乙烯、马来酸酐为连接组分,将二氧化钛接枝到聚（苯乙烯-二乙烯基苯）微球的表面,成功制备了无孔和多孔纳米复合微球。研究了硅烷偶联剂（KH560）和苯乙烯对二氧化钛在无孔微球表面的分散性和接枝数量以及支撑微球的多孔性质对接枝到微球内部的二氧化钛数量的影响。结果表明,KH560和苯乙烯能够提高二氧化钛在微球表面的分散性和稳定性,使二氧化钛以30-80nm的粒径接枝在微球表面。苯乙烯又能使二氧化钛在无孔微球表面的接枝数量从10.4%增大到20.4%。平均孔径为136nm的多孔微球为支撑微球得到的复合粒子中二氧化钛最高接枝量可达26%,明显高于无孔微球和平均孔径为31nm的多孔微球。     

Synthesis of TiO2 based on hydrothermal methods using elevated pressures and microwave conditions

Titanium dioxide (TiO₂), especially in its anatase form, is an effective photocatalyst under ultraviolet (UV) light. The particle size of TiO₂ is a critical factor to determine its photoactivity based on its quantum effectiveness under light irradiations. Thus, nanocrystalline TiO₂ has been widely accepted to significantly enhance this effect. The sol–gel method is generally used to synthesize the anatase form of nanocrystalline TiO₂. In this study, we expanded the synthesis method of TiO₂ to high pressures under direct heating (hydrothermal method) and indirect heating (microwave-assisted method). It was found that pH value is one of the major factors to control nano-sizes of TiO₂ particles, and the neutral condition in all methods is preferable for controlling the sizes of the prepared TiO₂ particles. The microwave-assisted method further improves quality of synthesized nano-size TiO₂ below 10 nm. These results have been confirmed by both the direct size measurement using TEM images and indirect determination using XRD peaks. The collected samples are further analyzed using UV–Vis spectroscopy to identify the particle size-dependent photoreactivity and to confirm the effectiveness of microwave-assisting under neutral conditions. DSC is also a powerful tool to identify the crystalline transition of TiO₂.     

Synthesis of nanosized TiO2/SiO2 particles using microwave processes and their photocatalytic activity on the decomposition of orange II

The nanosized titania and TiO₂/SiO₂ particles were prepared by the microwave-hydrothermal method. The effect of physical properties TTIP/TEOS ratio and calcination temperature has been investigated. The major phase of the pure TiO₂ particle is of the anatase structure, and a rutile peak was observed above 800°C. In TiO₂/SiO₂ particles, however, no significant rutile phase was observed, although the calcination temperature was 900°C. No peaks for the silica crystal phase were observed at either silica/titania ratio. The crystallite size of TiO₂/SiO₂ particles decreases as compared to pure TiO₂ at high calcination temperatures. The TiO₂/SiO₂ particles show higher activity on the photocatalytic decomposition of orange II as compared to pure TiO₂ particles.     

Remarkable Charge Separation and Photocatalytic Efficiency Enhancement through Interconnection of TiO2 Nanoparticles by Hydrothermal Treatment

Although tremendous effort has been directed to synthesizing advanced TiO₂, it remains difficult to obtain TiO₂ exhibiting a photocatalytic efficiency higher than that of P25, a benchmark photocatalyst. P25 is composed of anatase, rutile, and amorphous TiO₂ particles, and photoexcited electron transfer and subsequent charge separation at the anatase–rutile particle interfaces explain its high photocatalytic efficiency. Herein, we report on a facile and rational hydrothermal treatment of P25 to selectively convert the amorphous component into crystalline TiO₂, which is deposited between the original anatase and rutile particles to increase the particle interfaces and thus enhance charge separation. This process produces a new TiO₂ exhibiting a considerably enhanced photocatalytic efficiency. This method of synthesizing this TiO₂, inspired by a recently burgeoning zeolite design, promises to make TiO₂ applications more feasible and effective.     

Influence of TiO2 particles and APP on combustion behavior and mechanical properties of flame-retardant thermoplastic polyurethane

The experimental investigation on combustion behavior and mechanical properties of flame-retardant thermoplastic polyurethane were performed in the article. By the masterbatch-melt blending technique, the TiO₂ particles were well dispersed in TPU/APP composites. The microscopic morphology structure was observed by TEM and SEM. TEM images of TPU–TiO₂ masterbatch material showed that the grain sizes of TiO₂ particles were 200–400 nm. The SEM result indicated that the TiO₂ particles could enhance compatibility and dispersion of APP in TPU. The mechanical properties of TPU composites were characterized by dynamic mechanical analysis (DMA) and tensile tests, respectively. The DMA results indicated that TiO₂ particles could improve the viscoelastic property of the TPU/APP composites. The tensile strength achieved a significant improvement with addition of TiO₂ particles. APP/TiO₂-5 obtains a better value of 344% than APP-1 (277%). Also, the flame-retardant property and thermal stability of the TPU composites were characterized using cone calorimeter test (CCT) and thermogravimetric analysis (TGA), respectively. The CCT results revealed that TiO₂ particles could enhance the flame-retardant property of APP in TPU. The peak heat release rate of APP/TiO₂-4 containing 0.5% TiO₂ decreased to 157.27 kW m^?2 from 225.5 kW m^?2 of APP-1 sample without any TiO₂. The TiO₂ particles could promote the formation of carbon layers which restrict the diffusion of fuels into combustion zone and access of oxygen to the underlying materials. The TGA results indicated that TiO₂ can improve the thermal stability of TPU/APP composites.

     

Gas transport in TiO2 nanoparticle-filled poly(1-trimethylsilyl-1-propyne)

Titanium dioxide (TiO₂) nanoparticles were dispersed via solution processing in poly(1-trimethylsilyl-1-propyne) (PTMSP) to form nanocomposite films. Nanoparticle dispersion was investigated using atomic force microscopy and transmission electron microscopy. At low-particle loadings, nanoparticles were dispersed individually and in nanoscale aggregates. At high-particle loadings, some nanoparticles formed micron-sized aggregates. The gas transport and density exhibited a strong dependence on nanoparticle loading. At low-TiO₂ loadings, the composite density was similar to or slightly higher than that predicted by a two-phase additive model. However, at particle loadings exceeding approximately 7 nominal vol.%, the density was markedly lower than predicted, suggesting that the particles induced the creation of void space within the nanocomposite. For example, when the TiO₂ nominal volume fraction was 0.35, the polymer/particle composite density was 40% lower than expected based on a two-phase additive model for density. At low-nanoparticle loading, light gas permeability was lower than that of the unfilled polymer. At higher nanoparticle loadings, light gas permeability (i.e., CO₂, N₂, and CH₄) increased to more than four times higher than in unfilled PTMSP. At most, selectivity changed only slightly with particle loading.     

Structural and electrochemical characterization of polyaniline/LiCoO2 nanocomposites prepared via a Pickering emulsion

Polyaniline (PANI)/LiCoO₂ nanocomposite materials are successfully ready through a solid-stabilized emulsion (Pickering emulsion) route. The properties of nanocomposite materials have been put to the test because of their possible relevance to electrodes of lithium batteries. Such nanocomposite materials appear thanks to the polymerization of aniline in Pickering emulsion stabilized with LiCoO₂ particles. PANI has been produced through oxidative polymerization of aniline and ammonium persulfate in HCl solution. The nanocomposite materials of PANI/LiCoO₂ could be formed with low amounts of PANI. The morphology of PANI/LiCoO₂ nanocomposite materials shows nanofibers and round-shape-like morphology. It was found that the morphology of the resulting nanocomposites depended on the amount of LiCoO₂ used in the reaction system. Ammonium persulfate caused the loss of lithium from LiCoO₂ when it was used at high concentration in the polymerization recipe. Highly resolved splitting of 006/102 and 108/110 peaks in the XRD pattern provide evidence to well-ordered layered structure of the PANI/LiCoO₂ nanocomposite materials with high LiCoO₂ content. The ratios of the intensities of 003 and 104 peaks were found to be higher than 1.2 indicating no pronounced mixing of the lithium and cobalt cations. The electrochemical reactivity of PANI/LiCoO₂ nanocomposites as positive electrode in a lithium battery was examined during lithium ion deinsertion and insertion by galvanostatic charge–discharge testing; PANI/LiCoO₂ nanocomposite materials exhibited better electrochemical performance by increasing the reaction reversibility and capacity compared to that of the pristine LiCoO₂ cathode. The best advancement has been observed for the PANI/LiCoO₂ nanocomposite 5 wt.% of aniline.