Influence of the morphology and microstructure on the photocatalytic properties of titanium oxide films obtained by sparking anodization in H3PO4

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Titanium-oxide magneli phases in four chondritic porous interplanetary dust particles

Detailed analytical electron microscope analyses of four fine-grained chondritic porous interplanetary dust particles (IDPs)reveal the presence of titanium oxide Magneli phases, TinO2n-1 (n=4,5,6), and rare Ti-metal. The titanium minerals are indigenous to these chondritic IDPs. The association of Magneli phases, Ti-metal, and carbonaceous material in chondritic IDPs, along with the grain size distributions support in situ solid carbon gasification in these extraterrestrial particles. The active catalyst in this process is titanium metal that we infer may be of interstellar origin. This favorable catalysis uniquely leads to the formation of Magneli phases. As chondritic IDPs may be solid debris of short-period comets, our data indicate that nuclei of short-period comets may show distinctive chemical reactions that lead to Ti-mineral assemblages that typically include Magneli phases. The proposed model provides a plausible mechnism to explain the higher solid carbon content of chondritic IDPs relative to bulk carbon abundances typical for carbonaceous chondrite matrices that represent another type of more evolved, that is, metamorphosed, undifferentiated solar system bodies.

Enhanced photocatalytic activity of titanium oxide nanotubes after heating treatment

Titanium oxide nanotubes were obtained by an electrochemical anodization method. Scanning electron microscope results demonstrate that the diameter of the tubes is about 120 nm and the length of the tubes is around 13 μm. Transmission electron microscope results indicate that the nanotubes are assembled by numerous nanoparticles and tube-like structure remains well after heat treatment at 400-600 °C. The photocatalysis performance of the nanotubes was evaluated in terms of the decomposition rate of methyl orange under UV irradiation. The results show that the photocatalytic activity was enhanced through the heating treatment of the nanotubes, and the nanotubes heated at 600 °C exhibits the best photocatalytic activity. X-ray diffraction patterns indicate that there is no phase transformation during the heat treatment. Therefore, the enhanced activity can be attributed to the improvement of nanotubes crystallinity, which may provide more insights about the effect of the crystallinity on the photocatalytic performance.

Comparative study of photocatalytic performance of titanium oxide spheres assembled by nanorods, nanoplates and nanosheets

TiO2 spheres assembled by nanorods, nanoplates and nanosheets were fabricated by facile hydrothermal/solvothermal methods. The three samples were thoroughly characterised by scanning electron microscopy, X-ray diffraction, the Brunauer–Emmett–Teller method and UV spectroscopy. The surface area of spheres assembled by nanosheets was 83.9 m2g–1, which is larger than that obtained for nanorods (10.8 m2g–1) and nanoplates (6.31 m2g–1). Their photocatalytic performance was evaluated in terms of the decomposition rate of methyl orange in these three samples under UV irradiation. The best photoactivity was observed in the samples constructed from nanosheets.

One-step synthesis of titanium oxide with trilayer structure for dye-sensitized solar cells

Titanium oxide films with trilayer structure grown on fluorine doped tin oxide substrate were prepared from one-step hydrothermal process. The trilayer structure consists of microflowers, nanorod array and compact nanoparticulates, which is expected to possess the merits of good light harvesting, a high electron transport rate, while avoiding the issues of electron shunting. The photovoltaic performance was comprehensively studied and a 60% enhancement in short circuit photocurrent density was found from microflowers contribution as a light scattering layer. This unique trilayer structure exhibits great potential application in future dye-sensitized solar cells.

Growth of titanium oxide overlayers by thermal oxidation of titanium

This paper describes a theoretical model for the growth of titanium oxide by thermal oxidation of titanium. It is shown that this model can explain the formation of layers of different oxides of titanium and the changes in these layers with variations in the conditions of oxidation. Some experimental X-ray diffraction results which support the model are also given.

Microstructure control and wear of Al2O3-SiC-(Al,Si) composites made by melt oxidation

Ceramic matrix composites of Al2O3-SiC-(Al,Si) have been fabricated by directed melt oxidation of aluminum alloys into SiC particulate preforms. The proportions of Al2O3, alloy, and porosity in the composite can be controlled by proper selection of SLC particle size and the processing temperature. The wear resistance of composites was evaluated in pin-on-disk experiments against a hard steel substrate. Minimum wear rate comparable to conventional ceramics such as ZTA is recorded for the composition containing the highest fraction of alloy, owing to the development of a thin and adherent tribofilm with a low coefficient of friction.

Hot deformation behaviour and microstructure control in AlCrCuNiFeCo high entropy alloy

An AlCrCuNiFeCo high entropy alloy (HEA), which has simple face centered cubic (FCC) and body centered cubic (BCC) solid solution phases as the microstructural constituents, was processed and its high temperature deformation behaviour was examined as a function of temperature (700-1030 degrees C) and strain rate (10(-3)-10(-1) s(-1)), so as to identify the optimum thermo-mechanical processing (TMP) conditions for hot working of this alloy. For this purpose, power dissipation efficiency and deformation instability maps utilizing that the dynamic materials model pioneered by Prasad and co-workers have been generated and examined. Various deformation mechanisms, which operate in different temperature-strain rate regimes, were identified with the aid of the maps and complementary microstructural analysis of the deformed specimens. Results indicate two distinct deformation domains within the range of experimental conditions examined, with the combination of 1000 degrees C/10(-3) s(-1) and 1030 degrees C/10(-2) s(-1) being the optimum for hot working. Flow instabilities associated with adiabatic shear banding, or localized plastic flow, and or cracking were found for 700-730 degrees C/10(-3)-10(-1) s(-1) and 750-860 degrees C/10(-1.4)-10(-1) s(-1) combinations. A constitutive equation that describes the flow stress of AlCrCuNiFeCo alloy as a function of strain rate and deformation temperature was also determined. (C) 2014 Elsevier Ltd. All rights reserved.

Microstructure control and iodine doping of bismuth telluride

On the materials scale, thermoelectric efficiency is defined by the dimensionless figure of merit zT. This value is made up of three material components in the form zT = Tα²/ρκ, where α is the Seebeck coefficient, ρ is the electrical resistivity, and κ is the total thermal conductivity. Therefore, in order to improve zT would require the reduction of κ and ρ while increasing α. However due to the inter-relation of the electrical and thermal properties of materials, typical routes to thermoelectric enhancement come in one of two forms. The first is to isolate the electronic properties and increase α without negatively affecting ρ. Techniques like electron filtering, quantum confinement, and density of states distortions have been proposed to enhance the Seebeck coefficient in thermoelectric materials. However, it has been difficult to prove the efficacy of these techniques. More recently efforts to manipulate the band degeneracy in semiconductors has been explored as a means to enhance α.

The other route to thermoelectric enhancement is through minimizing the thermal conductivity, κ. More specifically, thermal conductivity can be broken into two parts, an electronic and lattice term, κ_e and κ_l respectively. From a functional materials standpoint, the reduction in lattice thermal conductivity should have a minimal effect on the electronic properties. Most routes incorporate techniques that focus on the reduction of the lattice thermal conductivity. The components that make up κ_l (κ_l = 1/3Cνl) are the heat capacity (C), phonon group velocity (ν), and phonon mean free path (l). Since the difficulty is extreme in altering the heat capacity and group velocity, the phonon mean free path is most often the source of reduction.

Past routes to decreasing the phonon mean free path has been by alloying and grain size reduction. However, in these techniques the electron mobility is often negatively affected because in alloying any perturbation to the periodic potential can cause additional adverse carrier scattering. Grain size reduction has been another successful route to enhancing zT because of the significant difference in electron and phonon mean free paths. However, grain size reduction is erratic in anisotropic materials due to the orientation dependent transport properties. However, microstructure formation in both equilibrium and nonequilibrium processing routines can be used to effectively reduce the phonon mean free path as a route to enhance the figure of merit.

This work starts with a discussion of several different deliberate microstructure varieties. Control of the morphology and finally structure size and spacing is discussed at length. Since the material example used throughout this thesis is anisotropic a short primer on zone melting is presented as an effective route to growing homogeneous and oriented polycrystalline material. The resulting microstructure formation and control is presented specifically in the case of In₂Te₃-Bi₂Te₃ composites and the transport properties pertinent to thermoelectric materials is presented. Finally, the transport and discussion of iodine doped Bi₂Te₃ is presented as a re-evaluation of the literature data and what is known today.

Sol-gel-derived titanium oxide/copolymer composite based glucose biosensor

A new type of sol-gel-derived titanium oxide/copolymer composite material was developed and used for the construction of glucose biosensor. The composite material merged the best properties of the inorganic species, titanium oxide and the organic copolymer, poly(vinyl alcohol) grafting 4-vinylpyridine (PVA-g-PVP). The glucose oxidase entrapped in the composite matrix retained its bioactivity. Morphologies of the composite-modified electrode and the enzyme electrode were characterized with a scanning electron microscope. The dependence of the current responses on enzyme-loading and pH was studied. The response time of the biosensor was < 20 s and the linear range was up to 9 mM with a sensitivity of 405 nA/mM. The biosensor was stable for at least I month. In addition, the tetrathiafulvalene-mediated enzyme electrode was constructed for the decrease of detection potential and the effect of three common physiological sources that might interfere was also investigated.

Studies on electrocatalytic performance of titanium oxide electrode modified with Pt toward the oxidation of methanol

Electrocatalytic performance of the Pr-TiOx/Ti electrode prepared with electrochemical reduction-oxidation method toward the oxidation of methanol has been studied, The experimental results showed that the Pt-TiOx/Ti electrode has a high electrocatalytic activity and good stability for the electrocatalytic oxidation of methanol, By means of electrochemical, XPS, STM and in-situ FTIR techniques, it was found that one reason for the electrode to exhibit an excellent performance is attributed to the high dispersion between nanosized Pt and TiOx particles, The low adsorption ability of the intermediate derived from methanol, such as linearly adsorbed CO species on the electrode surface due to the interaction between Pt and TiOx, also results in the excellent performance.

Amperometric tyrosinase biosensor based on a sol-gel-derived titanium oxide-copolymer composite matrix for detection of phenolic compounds

A new type of tyrosinase biosensor was developed for the detection of phenolic compounds, based on the immobilization of tyrosinase in a sol-gel-derived composite matrix that is composed of titanium oxide sol and a grafting copolymer of poly(vinyl alcohol) with 4-vinylpyridine. Tyrosinase entrapped in the composite matrix can retain its activity to a large extent owing to the good biocompatibility of the matrix. The parameters of the fabrication process and the variables of the experimental conditions for the enzyme electrode were optimized. The resulting sensor exhibited a fast response (20 s), high sensitivity (145.5 muA mmol(-1) 1) and good storage stability. A detection limit of 0.5 muM catechol was obtained at a signal-to-noise ratio of 3.

Electrocatalytic oxidation of methanol at the titanium oxide electrode modified with Pt microparticles

The electrocatalytic oxidation of methanol at the Titanium oxide (TiOx, x<2) film modified with Pt microparticles has been studied. The results show that the modified electrodes exhibit a significant electrocatalytic activity and good stability for the oxidation of methanol. Under the optimal conditions, the peak current density at 0.58 V for the oxidation of methanol in the positive-going sweep is about 526 mA/cm(2) at the scan rate of 5 mV/s in 0.5 mol/L CH3OH and 0.5 mol/L H2SO4 solution and the over potential of the methanol oxidation at the modified electrode increases about 30 similar to 40 mV after 70 minutes at the current density of 100 mA/cm(2) and 50 mA/cm(2). The enhanced electrocatalytic activity and good stability are ascribed to the high dispersion of Pt microparticles in and on the TiOx film and the synergistic effect between Pt microparticles and TiOx.