Síntese hidrotérmica e caracterização estrutural de titanatos nanotubulares para aplicação na captura do dióxido de carbono

Nanostructured materials have been spreading successfully over past years due its size and unusual properties, resulting in an exponential growth of research activities devoted to nanoscience and nanotechnology, which has stimulated the search for different methods to control main properties of nanomaterials and make them suitable for applications with high added value. In the late 90 s an alternative and low cost method was proposed from alkaline hydrothermal synthesis of nanotubes. Based on this context, the objective of this work was to prepare different materials based on TiO2 anatase using hydrothermal synthesis method proposed by Kasuga and submit them to an acid wash treatment, in order to check the structural behavior of final samples. They were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), adsorption/desorption of N2, thermal analysis (TG/DTA) and various spectroscopic methods such as absorption spectroscopy in the infrared (FT-IR), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). All the information of characterizations confirmed the complete conversion of anatase TiO2 in nanotubes titanates (TTNT). Observing the influence of acid washing treatment in titanates structure, it was concluded that the nanotubes are formed during heat treatment, the sample which was not subjected to this process also achieved a complete phase transformation, as showed in crystallography and morphology results, however the surface area of them practically doubled after the acid washing. By spectroscopy was performed a discussion about chemical composition of these titanates, obtaining relevant results. Finally, it was observed that the products obtained in this work are potential materials for various applications in adsorption, catalysis and photocatalysis, showing great promise in CO2 capture

Investigação da estabilidade térmica e das propriedades elétricas do TiO2 em função da dopagem com Ce(SO4)2

The metalic oxides have been studies due to differents applications as materials semiconductor in solar cells, catalysts, full cells and, resistors. Titanium dioxide (TiO2) has a high electric conductivity due to oxygen vacancies. The Ce(SO4)2.2H2O doped samples TiO2 and TiO2 pure was obtained sol-gel process, and characterized by X-ray diffractometry,thermal analysis, and impedance spectroscopy. The X-ray diffraction patterns for TiO2 pure samples shows at 700°C anatase phase is absent, and only the diffraction peaks of rutile phase are observed. However, the cerium doped samples only at 900°C rutile in the phase present with peaks of cerium dioxide (CeO2). The thermal analysis of the TiO2 pure and small concentration cerium doped samples show two steps weight loss corresponding to water of hydration and chemisorbed. To larger concentration cerium doped samples were observed two steps weight loss in the transformation of the doped cerium possible intermediate species and SO3. Finally, two steps weight loss the end products CeO2 and SO3 are formed. Analyse electric properties at different temperatures and concentration cerium doped samples have been investigated by impedance spectroscopy. It was observed that titanium, can be substituted by cerium, changing its electric properties, and increased thermal stability of TiO2 anatase structure

Obtenção e Caracterização Físico-Química do Sistema Compósito PEG-TiO2

Hybrid systems formed from polymers and transition metals have now their physical and chemical properties extensively investigated for use in electronic devices. In this work, Titanium Dioxide (TiO2) from the precursor of titanium tetrabutoxide and the composite system Poly(Ethylene Glycol)-Titanium Dioxide (TiO2-PEG) were synthesized by sol-gel method. The PEG as acquired and TiO2 and composites powders were analyzed by X-Ray Diffraction (XRD), Spectroscopy in the Infrared region with Fourier transform (IRFT), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM) and Electrochemical Impedance Spectroscopy (EIS). In the XRD analysis were observed in the TiO2 crystal faces of one of its polymorphs - anatase phase, crystal planes in Poly (Ethylene Glycol) with considerable intensity and in the composite systems the mixture of crystal faces of their precursors isolated and reduction of crystallinity. The TG / DTG suggested increasing the thermal instability of PEG in the composite powders as TiO2 is incorporated into the system. Spectral analysis presented in the infrared overlapping bands for the polymer and metal oxide, reducing the intensity of symmetric stretching of ligand groups in the main chain polymer and angular deformations; were observed using SEM micrographs of the morphological changes suffered by composite systems with the variation of the oxide concentration. Analyses by impedance spectroscopy indicated that the increased conductivity in composite occurs in line with the addition of the metal oxide concentration in the composite system

Estudo sobre a redução aluminotérmica de Ta2O5 e TiO2 usando descarga de cátodo oco

In this study it was used two metallic oxides, Ta2O5 and TiO2, in order to obtain metallic powders of Ta and Ti through aluminothermic reduction ignited by plasma. Ta2O5 and TiO2 powders were mixed with Al in a planetary mill, using different milling times. A thermal analysis study (DTA and TG) was carried out, in order to know the temperature to react both the mixtures. Then, these mixtures were submitted to a hollow cathode discharge, where they were reacted using aluminothermic reduction ignited by plasma. The product obtained was characterized by XRD and SEM, where it was proven the possibility of producing these metallic particles, different from the conventional process, where metallic ingots are obtained. It was verified that the aluminothermic reduction ignited by plasma is able to produce metallic powders of Ta and Ti, and a higher efficiency was observed to the process with Ta2O5-Al mixtures. Among different microstructural aspects observed, it can be noted the presence of metallic nanoparticles trapped into an Al2O3 matrix, besides acicular structures (titanium) and dendritic structures (tantalum), which are a product characteristic from a fast cooling

Síntese hidrotérmica assistida por micro-ondas de tiO2, e aplicação em nanocompósito

In recent decades have seen a sharp growth in the study area of nanoscience and nanotechnology and is included in this area, the study of nanocomposites with self-cleaning properties. Since titanium dioxide (TiO2) has high photocatalytic activity and also antimicrobial, self-cleaning surfaces in your application has been explored. In this study a comparison was made between two synthesis routes to obtain TiO2 nanoparticles by hydrothermal method assisted by microwave. And after analysis of XRD and SEM was considered the best material for use in nanocomposites. It was deposited nanocomposite film of poly (dimethyl siloxane) (PDMS) with 0.5, 1, 1.5 and 2% by weight of nanoparticles of titanium dioxide (TiO2) by the spraying method. The nanocomposite was diluted with hexane and the suspension was deposited onto glass substrate, followed by curing in an oven with forced air circulation. The photocatalytic activity of the nanocomposite impregnated with methylene blue was evaluated by UV- vis spectroscopy from the intensity variation of absorption main peak at 660nm with time of exposure to the UV chamber. Changes in the contact angle and microhardness were analyzed before and after UV aging test. The effect of ultraviolet radiation on the chemical structure of the PDMS matrix was evaluated by spectrophotometry Fourier transform infrared (FTIR).The results indicated that the addition of TiO2 nanoparticles in the coating PDMS gave high photocatalytic activity in the decomposition of methylene blue, an important characteristic for the development of self-cleaning coatings

A intervenção estatal no domínio econômico privado através da nova lei de recuperação de empresas e falências (lei 11.101/05)

Analysis of the elements of the Constitutional Order of the letter 1988 politics, with emphasis in the principles of this, a study on the intervention of the State in the private initiative by means of the Law of Recovery of Companies and Bankruptcies (law 11.101/05). New enterprise vision is admitted, over all in the interdependence between economic and social factors. Study on the globalization and the interdependence of economic and legal sciences in the construction of a legal optics in the search for the economic and social development, with the recognition of the interference of the Economy in the Right and its uneven importance. Still, we delineate the state intervention in the economic scope, of company and in the judicial recovery, as well as the consequences of such intervention in the involved credits in the judicial recovery and patrimony of the debtor in recovery. For such task, the elements of the Judicial Recovery, its principles and adequacy of these to the related ones in the chapter had been analyzed that turns on the national economic Order, describing the formal procedure for concession of the benefit of the Judicial Recovery and the principles in existing them. The forms of intervention of the State in the private economy were not disrespected, relating its direct and indirect performance as half of preservation of interests writings in the constitutional scope as public interest and preservation of the National economic Order. The regulating agencies as of direct state intervention were half not disrespected of the study for the relevance of the subject. It is revised national bibliography with incursions in French, Portuguese and North American comparative jurisprudence. One contributes in the aspect of the paper of the Judiciary Power in the protection of the companies in crisis and the social and economic impacts, over all in relation to the rights of the worked ones, credit and enterprise

Redução carbotérmica de TiO2 por descarga em cátodo oco

In this study we used the plasma as a source of energy in the process of carbothermic reduction of rutile ore (TiO2). The rutile and graphite powders were milled for 15 h and placed in a hollow cathode discharge produced by in order to obtain titanium carbonitride directly from the reaction, was verified the influence of processing parameters of plasma temperature and time in the synthesis of TiCN. The reaction was carried out at 600, 700 and 800˚C for 3 to 4 hours in an atmosphere of nitrogen and argon. During all reactions was monitored by plasma technique of optical emission spectroscopy (EEO) to check the active species present in the process of carbothermal reduction of TiO2. The powder obtained after the reactions were characterized by the techniques of X-ray diffraction (XRD) and scanning electron microscopy (SEM). The technique of EEO were detected in all reactions the spectra CO and NO, and these gas-phase resulting from the reduction of TiO2. The results of X-ray diffraction confirmed the reduction, where for all conditions studied there was evidence of early reduction of TiO2 through the emergence of intermediate oxides. In the samples reduced at 600 and 700˚C, there was only the phase Ti6O11, those reduced to 800˚C appeared Ti5O9 phases, and Ti6O11 Ti7O13, confirming that the carbothermal reduction in plasma, a reduction of the ore rutile (TiO2) in a series of intermediate titanium oxide (TinO2n-1) where n varies between 5 and 10

Estudo de titanatos nanoestruturados obtidos por tratamento hidrotérmico de óxido de titânio em meio alcalino

TiTanate NanoTubes (TTNT) were synthesized by hydrothermal alkali treatment of TiO2 anatase followed by repeated washings with distinct degrees of proton exchange. TTNT samples with different sodium contents were characterized, as synthesized and after heattreatment (200-800ºC), by X-ray diffraction, scanning and transmission electron microscopy, electron diffraction, thermal analysis, nitrogen adsorption and spectroscopic techniques like FTIR and UV-Vis diffuse reflectance. It was demonstrated that TTNTs consist of trititanate structure with general formula NaxH2−xTi3O7·nH2O, retaining interlayer water in its multiwalled structure. The removal of sodium reduces the amount of water and contracts the interlayer space leading, combined with other factors, to increased specific surface area and mesopore volume. TTNTs are mesoporous materials with two main contributions: pores smaller than 10 nm due to the inner volume of nanotubes and larger pores within 5-60 nm attributed to the interparticles space. Chemical composition and crystal structure of TTNTs do not depend on the average crystal size of the precursor TiO2-anatase, but this parameter affects significantly the morphology and textural properties of the nanostructured product. Such dependence has been rationalized using a dissolution-recrystallization mechanism, which takes into account the dissolution rate of the starting anatase and its influence on the relative rates of growth and curving of intermediate nanosheets. The thermal stability of TTNT is defined by the sodium content and in a lower extent by the crystallinity of the starting anatase. It has been demonstrated that after losing interlayer water within the range 100-200ºC, TTNT transforms, at least partially, into an intermediate hexatitanate NaxH2−xTi6O13 still retaining the nanotubular morphology. Further thermal transformation of the nanostructured tri- and hexatitanates occurs at higher or lower temperature and follows different routes depending on the sodium content in the structure. At high sodium load (water washed samples) they sinter and grow towards bigger crystals of Na2Ti3O7 and Na2Ti6O13 in the form of rods and ribbons. In contrast, protonated TTNTs evolve to nanotubes of TiO2(B), which easily convert to anatase nanorods above 400ºC. Besides hydroxyls and Lewis acidity typical of titanium oxides, TTNTs show a small contribution of protonic acidity capable of coordinating with pyridine at 150ºC, which is lost after calcination and conversion into anatase. The isoeletric point of TTNTs was measured within the range 2.5-4.0, indicating behavior of a weak acid. Despite displaying semiconductor characteristics exhibiting typical absorption in the UV-Vis spectrum with estimated bandgap energy slightly higher than that of its TiO2 precursor, TTNTs showed very low performance in the photocatalytic degradation of cationic and anionic dyes. It was concluded that the basic reason resides in its layered titanate structure, which in comparison with the TiO2 form would be more prone to the so undesired electron-hole pair recombination, thus inhibiting the photooxidation reactions. After calcination of the protonated TTNT into anatase nanorods, the photocatalytic activity improved but not to the same level as that exhibited by its precursor anatase

Confecção e caracterização físico-química de filmes compósitos autossustentáveis NaAlg-TiO2-WO3

A new self-sustainable film was prepared through the sol-gel modified method, previously employed in our research group; sodium alginate was used as the polymer matrix, along with plasticizer glycerol, doped with titanium dioxide (TiO2) and tungsten trioxide (WO3). By varying WO3 concentration (0,8, 1,6, 2,4 and 3,2 μmol) and keeping TiO2 concentration constant (059 mmol), it was possible to study the contribution of these oxides on the obtained films morphological and electrical properties. Self-sustainable films have analyzed by Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XDR), Scanning Electron Microscope (SEM), Energy Dispersive X-ray Spectroscopy (EDS) and Electrochemical Impedance Spectroscopy (EIS). By the IR specters, it was possible identify the TiO2, and posteriorly WO3, addition has provided dislocation of alginate characteristics bands to smaller vibrations frequencies indicating an electrostatic interaction between the oxides and the polymer matrix. Diffractograms show predominance of the amorphous phase in the films. SEM, along with EDX, analysis revealed self-sustainable films showed surface with no cracks and relative dispersion of the oxides throughout the polymer matrix. From Impedance analysis, it was observe increasing WO3 concentration to 2,4 μmol provided a reduction of films resistive properties and consequent improvement of conductive properties

Obtenção e caracterização do sistema compósito alginato de sódio-dióxido de titânio em formas de pó e de membrana

The alginates are copolymers of 1→4-linked β-D-mannuronic acid (M) and α-Lguluronic acid (G) residues that are arranjed in a block structure along a linear chain. Titanium dioxide, TiO2, is a ceramic material and can exist in three distinct crystallography forms: anatase, brookite and rutile. composites of organic and inorganic materials have better properties than the components alone. Thus, this study aims to synthesize, characterize and analyze the composite NaAlg-TiO2 in the form of powder and film. The synthesis of composite powders was performed using the sol-gel process and obtain the composite film was performed using the slow evaporation process, then the composites were analyzed by infrared spectroscopy, fluorescence x ray, thermal analysis, attenuated total reflection (ATR), x ray diffraction and impedance spectroscopy. The X ray diffraction patterns of composite powders show that with increasing calcination temperature, there were no complete transition of rutile-anatase crystalline phase, since at all temperatures studied (300, 500, 700, 900 and 1100ºC) were observed peaks of anatase phase. Thermal analysis shows that at 400°C caused the decomposition of sodium alginate in sodium carbonate and above 600°C, we observe an exothermic peak related to the decomposition of sodium carbonate and in the presence of titanium dioxide becomes sodium titanate. The XRD results confirm the formation of sodium carbonate at 700ºC and the formation sodium titanate in the temperature range 900-1100ºC. The sodium titanate influenced the electrical properties of the material, because with increasing temperature there was a decrease in conductivity, probably due to the creation of Ti vacancies, since the sodium can induce the reduction of surface Ti4+ ions into Ti3+ species. The infrared spectra of the composites in the form of powder and film showed a small shift in the bands compared to the spectrum of pure alginate, indicating that these shifts, even small ones, have evidence of miscibility between the polymer and ceramic material