Electrolytic treatment of wastewater containing n-phenyl-n '-1,3-dimethylbutyl-p-phenylenediamine

This study investigated the effects of electrolytic treatment using Dimensionally Stable Anode (DSA, 70%TiO2/30%RuO2) type electrodes in simulated wastewater containing aromatic amine n-phenyl-n'-1,3-dimethylbutyl-p-phenylenediamine (Flexzone 7P). A low direct current density of 0.025 A cm(-2) was applied for periods up to 60 minutes and a 52.6% decrease in Flexzone 7P concentration was observed. Ultraviolet-visible spectra, gas chromatography, toxicity and biodegradation tests were carried out with the aim of verifying the toxic by-products that were formed. Ultraviolet-visible spectra of simulated wastewater exhibited changes in the aromatic amine's molecular structure. Additionally, based on the S. cerevisiae toxicity test, it was observed that detoxification of the wastewater occurred after 15 minutes of electrolysis. It was also observed that five minutes of treatment were sufficient to improve the biodegradation rate, determined through the respirometric Bartha method.

Pore size evolution during sintering of ceramic oxides

This paper reviews the influence of particle size distribution, agglomerates, rearrangement, sintering atmospheres and impurities on the pore evolution of some commonly studied oxides. These factors largely affect sintering mechanisms due to modifications of diffusion coefficients or evaporation-condensation. Very broad particle size distribution leads to grain growth and agglomerates densify first. Rearrangement of particles due to neck asymmetry mainly in the early stage of sintering is responsible for a high rate of densification in the first minutes of sintering by collapse of large pores. Sintering atmospheres play an important role in both densification and pore evolution. The chemical interaction of water molecules with several oxides like MgO, ZnO and SnO2 largely affects surface diffusion. As a consequence, there is an increase in the rates of pore growth and densification for MgO and ZnO and in the rate of pore growth for SnO2. Carbon dioxide does not affect the rate of sintering of MgO but greatly affects both rates of pore growth and densification of ZnO. Oxygen concentration in the atmosphere can especially affect semiconductor oxides but significantly affects the rate of pore growth of SnO2. Impurities like chlorine ions increase the rate of pore growth in MgO due to evaporation of HCl and Mg(OH)Cl, increasing the rate of densification and particle cuboidization. CuO promotes densification in SnO2, and is more effective in dry air. The rate of densification decrease and pore widening are promoted in argon. An inert atmosphere favors SnO2 evaporation due to reduction of CuO. © 1990.

Effect of cobalt(II) oxide and manganese(IV) oxide on sintering of tin(IV) oxide

Additions of 0.5 to 2.0 mol% of CoO or MnO2 onto SnO, promote densification of this oxide up to 99% of theoretical density. The temperature of the maximum shrinkage rate (TM) and the relative density in the maximum densification rate (p*) during constant sintering heating rate depend on the dopant concentration. Thus, dopant concentration controls the densifying and nondensifying mechanisms during sintering. The densification of SnO2 witih addition of CoO or MnO, is explained in terms of the creation of oxygen vacancies.

An improved three-dimensional model for growth of oxide films induced by laser heating

In this paper we consider a three-dimensional heat diffusion model to explain the growth of oxide films which takes place when a laser beam is shined on and heats a metallic layer deposited on a glass substrate in a normal atmospheric environment. In particular, we apply this model to the experimental results obtained for the dependence of the oxide layer thickness on the laser density power for growth of TiO2 films grown on Ti-covered glass slides. We show that there is a very good agreement between the experimental results and the theoretical predictions from our proposed three-dimensional model, improving the results obtained with the one-dimensional heat diffusion model previously reported. Our theoretical results also show the occurrence of surface cooling between consecutive laser pulses, and that the oxide track surface profile closely follows the spatial laser profile indicating that heat diffusive effects can be neglected in the growth of oxide films by laser heating. © 2001 Elsevier Science B.V.

Dental implants: Surface modification of cp-Ti using plasma spraying and the deposition of hydroxyapatite

The commercial pure titanium (cp-Ti) is currently being used with great success in dental implants. In this work we investigate how the cp-Ti implants can be improved by modifying the metal surface morphology, on which a synthetic material with properties similar to that of the inorganic part of the bone, is deposited to facilitate the bone/implant bonding. This synthetic material is the hydroxyapatite, HA, a calcium-phosphate ceramic. The surface modification consists in the application of a titanium oxide (TiO2) layer, using the thermal aspersion - plasma spray technique, with posterior deposition of HA, using the biomimetic method. The X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray (EDX) and Diffuse Reflectance Infrared Fourier Transform (DRIFT) techniques have been used for characterizing phases, microstructures and morphologies of the coatings. The TiO2 deposit shows a mixture of anatase, rutilo and TiO2-x phases, and a porous and laminar morphology, which facilitate the HA deposition. After the thermal treatment, the previously amorphous structured HA coating, shows a porous homogeneous morphology with particle size of about 2-2.5 μm, with crystallinity and composition similar to that of the biological HA.

Photoelectrocatalytic degradation of Remazol Brilliant Orange 3R on titanium dioxide thin-film electrodes

Degradation of reactive dye Remazol Brilliant Orange 3R (RBO) has been performed using photoeletrocatalysis. A biased potential is applied across a titanium dioxide thin-film photoelectrode illuminated by UV light. It is suggested that charges photogenerated at the electrode surface give rise to chlorine generation and powerful oxidants (OH) that causes the dye solution to decolorize. Rate constants calculated from color decay versus time reveal a first-order reaction up to 5.0×10-5 mol l-1 in dye concentration. The best experimental conditions were found to be pH 6.0 and 1.0 mol l-1 NaCl when the photoelectrode was biased at +1V (versus SCE). Almost complete mineralization of the dye content (70% TOC reduction) was achieved in a 3-h period using these conditions. Effects of other electrolytes, dye concentration and applied potentials also have been investigated and are discussed. © 2003 Elsevier Science B.V. All rights reserved.

Behavior of bromide in the photoelectrocatalytic process and bromine generation using nanoporous titanium dioxide thin-film electrodes

In this study, the photoelectrocatalytic behavior of bromide and generation of bromine using TiO2 was investigated in the separate anode and cathode reaction chambers. Our results show that the generation of bromine begins around a flatband potential of -0.34 V vs. standard calomel electrode (SCE) at pH 3.0 under UV illumination and increases with an increase in positive potential, finally reaching a steady-state concentration at 1.0 V vs. SCE. Maximum bromine formation occurs over the range of pH 4-6, decreasing sharply at conditions where the pH > 7. © 2003 Elsevier Ltd. All rights reserved.

Photoelectrocatalytic production of active chlorine on nanocrystalline titanium dioxide thin-film electrodes

The production of chlorine and hypochlorite is of great economical and technological interest due to their large-scale use in many kinds of commercial applications. Yet, the current processes are not without problems such as inevitable side reactions and the high cost of production. This work reports the photoelectrocatalytic oxidation of chloride ions to free chlorine as it has been investigated by using titanium dioxide (TiO2) and several metal-doped titanium dioxide (M-TiO2) material electrodes. An average concentration of 800 mg L-1 of free chlorine was obtained in an open-air reactor using a TiO2 thin-film electrode biased at +1.0 V (SCE) and illuminated by UV light. The M-doped electrodes have performed poorly compared with the pure TiO2 counterpart. Test solutions containing 0.05 mol L-1 NaCl pH 2.0-4.0 were found to be the best conditions for fast production of free chlorine. A complete investigation of all parameters that influence the global process of chlorine production by the photoelectrocatalytic method such as applied potential, concentration of NaCl, pH solution, and time is presented in detail. In addition, photocurrent vs potential curves and the reaction order are also discussed.

Nucleation and crystallization of titania nanoparticles in silica titania planar waveguides: A study by low frequency Raman scattering

SiO2 (1-x) - TiO2 (x) waveguides, with the mole fraction x in the range 0.07 - 0.20 and thickness of about 0.4 μm, were deposited on silica substrates by a dip-coating technique. The thermal treatments at 700-900°C, used to fully densify the xerogels, produce nucleation of TiO2 nanocrystals even for the lowest TiO2 content. The nucleation of TiO2 nanocrystals and their growth by thermal annealing up to 1300°C were studied by waveguide Raman spectroscopy, for the SiO2 (0.8) - TiO2 (0.2) composition. By increasing the annealing temperature, the Raman spectrum evolves from that typical of the silica-titania glass to that of anatase, but brookite phase is dominant at intermediate temperatures. In the low. frequency region (5-50 cm-1) of the Raman spectra, acoustic vibrations of the nanocrystals are observed. From the measured line shapes, we can deduce the size distribution of the particles. The results are compared with those obtained from the line widths in the X-ray diffraction patterns. Nanocrystals with a mean size in the range 4-20 nm are obtained, by thermal annealing in a corresponding range of 800-1300°C.

Densification of Mn-doped tin oxide films by conventional heating and microwave heating treatment

Mn(II) doped SnO2 thin films used for shielding fluoride glasses against corrosion were investigated by x-ray absorption spectroscopy (EXAFS and XANE)S at the Sn and Mn K-edges. The effect of firing treatment on the densification of the films was studied. It has been evidenced a partial change of Mn valence from 2.3 to 2.6 upon heating which is attributed to a change of ratios of two Mn sites: grafted divalent Mn ions at the surface of SnO 2 nanocrystallites and trivalent Mn ions embedded into a substitutional solid solution with Sn. © Physica Scripta 2005.

As rochas intrusivas da Formação Serra Geral na Porção leste da Bacia do Paraná no Estado de São Paulo: Aspectos petrográficos e geoquímicos - Resultados preliminares

The purpose of this paper is to present preliminary aspects of the petrography and chemistry of intrusive rocks (sills and dykes) from the eastern portion of the Parana Basin in the State of Säo Paulo. Data from 80 samples of the region show a subaphyric and subophitic nature and have plagioclase (25-50%), augite (3-39%), pigeonite (0-10%) and magnetite (4-20%) as an essential minerals. Apatite and quartz are present as accessory minerals. The geochemical data of intrusive rocks show a basic to intermediate composition (48% < SiO 2 < 56%) and a high Ti nature (TiO 2 > 2%). Based on the minor and trace composition of the intrusive rocks, two different magma types were recognized, named Paranapanema and Pitanga. The spatial distribution of these magma types is not alleatory in the studied region. The intrusive rocks of Pitanga magma type are displayed in the Campinas-Paulinia region, while the Paranapanema magma type cover a large region above that one, between Rio Claro and Cajuru. Furthermore, the chemical composition of the lava flows of the Serra Geral Formation, sampled in this work, reveals a magma of Urubici type. So, the intrusive rocks of the eastern portion of the of State Säo Paulo are not the extension of the lava flows, or they aren't a portions which don't reach the surface.

Photodegradation of soluble and emulsive cutting fluids using TiO 2 as catalyst

This paper describes results of the photo-degradation of three types of soluble and emulsive cutting fluids in an aqueous medium, using TiO2 as catalyst in suspension and UV radiation. The TiO2 proved to be an effective catalyst for the degradation of the cutting fluids investigated. The degradation rate depends on pH and nature of the fluids. The best performance of catalyst was observed at pH 8.0 for all the fluids when most of 70% of the organic load was decomposed. ©2006 Sociedade Brasileira de Química.

Mechanochemical synthesis of Bi4Ti3O12

Our efforts were directed to the preparation of bismuth titanate - Bi 4e;Ti3O12 (BIT) by mechanically assisted synthesis. The mechanical activation was applied to prepare bismuth titanate, Bi4e;Ti3O12, from bismuth oxide, Bi 2O3, and titanium oxide, TiO2 (in an anatase crystal form). Mechanochemical synthesis was performed in a planetary ball mill in air atmosphere. Bismuth titanate ceramics was obtained by sintering at 1000° C The formation of Bi4e;Ti3O12 in the sintered samples was confirmed by X-ray diffraction analysis. Scanning electron microscopy, SEM, was used to study the particle size and powder morphology. The obtained results indicate that Bi4e;Ti3O12 from the powder synthesized by high-energy ball milling exhibits good sinterability, showing advantage of the mechanochemical process over conventional solid-state reaction.

Effect of scandium on the structural and photocatalytic properties of titanium dioxide thin films

Pure and scandium doped-TiO2 thin films were prepared by the sol-gel process and coated by dip coating. The effects of scandium on the phase formation, optical properties and photoactivity of the TiO2 thin films were investigated. The lattice parameters and the crystallinity of the anatase phase, characterized by the Rietveld method, demonstrated that scandium doping affected the structural parameters and crystallinity of the films, modifying the absorption edge. A direct correlation was found between band gap energy and photodegradation efficiency, with lower values of band gap energy augmenting this efficiency. Moreover, a significant improvement in the catalyst's photodegradation efficiency was attained with a scandium concentration of 5.0 mol%. © 2007 Springer Science+Business Media, LLC.

Heating rate and temperature effects on the BaTiO3 formation by thermal decomposition of (Ba,Ti) organic precursors during the Pechini process

Different thermal treatments for the synthesis of BaTiO3 powder obtained through the Pechini method were studied. The synthesis of BaTiO3 starts at 150 °C by the thermal dehydration of organic precursors. The usual inevitable formation of barium carbonate during the thermal decomposition of the precursor could be retarded at lower calcination temperatures and optimized heating rates. The organic precursors were treated at temperatures between 200 and 400 °C. Then, the samples were calcined at 700 and 800 °C for 4 and 2 h, respectively. The resulting ceramic powders were characterized by gravimetric and differential thermal analyses, X-ray powder diffraction and infrared spectroscopy. It was found that depending on the heating rate and final temperature of the thermal treatment, high amounts of BaCO3 and TiO2 could be present due to the high concentration of organics in the final calcination step. © 2007 Elsevier B.V. All rights reserved.