Tetragonal to monoclinic phase transition observed during Zr anodisation

Plasma electrolytic oxidation (PEO) is a coating procedure that utilises anodic oxidation in aqueous electrolytes above the dielectric breakdown voltage to produce oxide coatings that have specific properties. These conditions facilitate oxide formation under localised high temperatures and pressures that originate from short-lived microdischarges at sites over the metal surface and have fast oxide volume expansion. Anodic ZrO2 films were prepared by subjecting metallic zirconium to PEO in acid solutions (H2C 2O4 and H3PO4) using a galvanostatic DC regime. The ZrO2 microstructure was investigated in films that were prepared at different charge densities. During the anodic breakdown, an important change in the amplitude of the voltage oscillations at a specific charge density was observed (i.e., the transition charge density (Q T)). We verified that this transition charge is a monotonic function of both the current density and temperature applied during the anodisation, which indicated that Q T is an intrinsic response of this system. The oxide morphology and microstructure were characterised using SEM and X-ray diffraction experiments (XRD) techniques. X-ray diffraction analysis revealed that the change in voltage oscillation was correlated with oxide microstructure changes during the breakdown process. © 2012 Springer-Verlag Berlin Heidelberg.

Degradation of dipyrone via advanced oxidation processes using a cerium nanostructured electrocatalyst material

This work studied the degradation of dipyrone, via electrochemical processes and via electro-Fenton reaction using a 4% CeO2/C gas diffusion electrode (GDE) prepared via modified polymeric precursor method. This material was used to electrochemically generate H2O2 through oxygen reduction. The mean crystallite sizes estimated by the Scherrer equation for 4% CeO2/C were 4 nm for CeO2-x (0 4 4) and 5 nm for CeO2 (1 1 1) while using transmission electron microscopy (TEM) the mean nanoparticle size was 5.4 nm. X-ray photoelectron spectroscopy (XPS) measurements revealed nearly equal concentrations of Ce(III) and Ce(IV) species on carbon, which contained high oxygenated acid species like CO and OCO. Electrochemical degradation using Vulcan XC 72R carbon showed that the dipyrone was not removed during the two hour electrolysis in all applied potentials by electro-degradation. Besides, when the Fenton process was employed the degradation was much similar when using cerium catalysts but the mineralization reaches just to 50% at -1.1 V. However, using the CeO2/C GDE, in 20 min all of the dipyrone was degraded with 26% mineralization at -1.3 V and when the Fenton process was employed, all of the dipyrone was removed after 5 min with 57% mineralization at -1.1 V. Relative to Vulcan XC72R, ceria acts as an oxygen buffer leading to an increase in the local oxygen concentration, facilitating H2O2 formation and consequently improving the dipyrone degradation © 2013 Elsevier B.V. All rights reserved.

Ethanol electro-oxidation in an alkaline medium using Pd/C, Au/C and PdAu/C electrocatalysts prepared by electron beam irradiation

Carbon-supported Pd, Au and bimetallic PdAu (Pd:Au 90:10, 50:50 and 30:70 atomic ratios) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their catalytic activities toward ethanol electro-oxidation were evaluated in an alkaline medium using electrochemical techniques, in situ attenuated total reflectance Fourier transformed infrared spectroscopy (ATR-FTIR) analysis and a single alkaline direct ethanol fuel cell (ADEFC). EDX analyses showed that the actual Pd: Au atomic ratios were very similar to the nominal ones. X-ray diffractograms of PdAu/C electrocatalysts evidenced the presence of Pd-rich (fcc) and Au-rich (fcc) phases. TEM analysis showed a homogeneous dispersion of nanoparticles on the carbon support, with an average size in the range of 3-5 nm and broad size distributions. Cyclic voltammetry (CV) and chronoamperometry (CA) experiments revealed the superior ambient activity toward ethanol electro-oxidation of PdAu/C electrocatalysts with Pd: Au ratios of 90:10 and 50:50. In situ ATR-FTIR spectroscopy measurements have shown that the mechanism for ethanol electro-oxidation is dependent on catalyst composition, leading to different reaction products, such as acetaldehyde and acetate, depending on the number of electrons transferred. Experiments on a single ADEFC were conducted between 50 and 900 C, and the best performance of 44 mW cm-2 in 2.0molL-1 ethanol was obtained at 850C for the Pd:Au 90:10 catalysts. This superior performance is most likely associated with enhancement of ethanol adsorption on Pd, oxidation of the intermediates, the presence of gold oxide-hydroxyl species, low mean particle diameters and better distribution of particles on the support. © 2013 Elsevier Ltd. All rights reserved.

Low tungsten content of nanostructured material supported on carbon for the degradation of phenol

A comparative study using different mass proportions of WO3/C (1%, 5%, 10% and 15%) for H2O2 electrogeneration and subsequent phenol degradation was performed. To include the influence of the carbon substrate and the preparation methods, all synthesis parameters were evaluated. The WO3/C materials were prepared by a modified polymeric precursor method (PPM) and the sol-gel method (SGM) on Vulcan XC 72R and Printex L6 carbon supports, verifying the most efficient metal/carbon proportion. The materials were physically characterized by X-ray diffraction (XRD) and by X-ray photoelectron spectroscopy (XPS) techniques. The XRD and the XPS techniques identified just one phase containing WO3 and elevated oxygen concentration on carbon with the presence of WO3. The oxygen reduction reaction (ORR), studied by the rotating ring-disk electrode technique, showed that WO3/C material with the lowest tungsten content (1% WO3/C), supported on Vulcan XC 72R and prepared by SGM, was the most promising electrocatalyst for H2O2 electrogeneration. This material was then analyzed using a gas diffusion electrode (GDE) and 585mgL-1 of H2O2 was produced in acid media. This GDE was employed as a working electrode in an electrochemical cell to promote phenol degradation by an advanced oxidative process. The most efficient method applied was the photo-electro-Fenton; this method allowed for 65% degradation and 11% mineralization of phenol during a 2-h period. Following 12h of exhaustive electrolysis using the photo-electro-Fenton method, the total degradation of phenol was observed after 4h and the mineralization of phenol approached 75% after 12h. © 2013 Elsevier B.V.

Aplicação do processo eletrolítico no tratamento de efluentes de uma indústria de recuperação de filmes plásticos pós-consumo

Pós-graduação em Engenharia Civil e Ambiental - FEB

Sistema de controle baseado em lógica fuzzy para regulagem de temperatura em aquecedor de óleo térmico da planta de anodo verde da Albrás

Neste trabalho são apresentados os resultados de uma técnica que permitiu implementar a estratégia de controle de temperatura do aquecedor de óleo térmico da fabrica de Anodo Verde da Albrás Alumínio Brasileiro S/A. No projeto utilizou-se um sistema hierarquizado baseado em conjuntos e lógica Fuzzy. O uso dessa metodologia fez com que o sistema fosse capaz de reagir adequadamente diante das variações do ponto de operação do aquecedor, pois o controle Fuzzy exibe algumas características do aprendizado humano, sendo considerado um exemplo de inteligência artificial. O aquecedor de óleo térmico é fundamental no processo de fabricação de blocos inódicos, utilizados como pólo positivo no processo de eletrólise na obtenção do alumínio primário. O sistema de óleo térmico aquece os misturadores e pré-aquecedor de coque, mantendo a temperatura desses equipamentos dentro dos limites estabelecidos pela engenharia de processo. A variável temperatura impacta diretamente na energia de mistura da pasta e na qualidade do produto final, que é o bloco anódico. A metodologia apresentada permitiu alcançar um controle de temperatura que atendeu satisfatoriamente os parâmetros de processo. O programa foi desenvolvido em linguagem ladder é executado em controladores lógicos programáveis (CLP’S) da Rockwell Automation. O controle já está em plena operação nas fábricas de anodos e os resultados obtidos demonstram a eficácia e viabilidade do sistema, que futuramente estará sendo implementado no controle de outros equipamentos da Albrás.

Estudos da lesão ao DNA por corantes têxteis e da capacidade protetora de flavonóides empregando biossensor eletroquímico: Carolina Venturini Uliana. -

Pós-graduação em Química - IQ

Electrochemical investigations on the capacity of flavonoids to protect DNA against damage caused by textile disperse dyes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Investigação dos efeitos das impurezas alcalinas e hidrogênio no quartzo submetido à eletrodifusão e radiação ionizante

Pós-graduação em Ciência dos Materiais - FEIS

Aspectos técnico, econômicos e ecológicos de processos de produção de hidrogênio

Pós-graduação em Engenharia Mecânica - FEG

Impact of the Textile Dye Acid Blue 40 on the Periphyton of a Simulated Microecosystem

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Degradation of dipyrone by electrogenerated H2O2 combined with Fe2+ using a modified gas diffusion electrode

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Tratamento da superfície do alumínio via eletrólise a plasma

This paper presents the study on the application of the electrolytic plasma for surface treatment of aluminum. A bibliographical study on the material of interest was preliminarily performed and later designed and built an electrolytic cell, including the excitation source. Unlike conventional electrolysis process, the plasma assisted carry on in the non-linear region of characteristic current/voltage curve. Therefore it requires for the on set of the process that the power supply operates on harder conditions than those on high current process. The plasma produced during the present investigation has temperatures in the range o 6,0.10 3 -7,0 .10 3 K, well above those found in conventional chemical process. It also shows a particular dynamic to promote changes on surface and to produce new materials. The plasma is generated by microdischarge in vapor or gas bubbles involved in physic-chemical processes in electrode regions of the electrolytic cell. The electrode material was the aluminum (7075). The Process Electrolytic Plasma Processing (EPP) is sensitive to various parameters such as operating voltage, current density, electrolyte, concentration of electrolyte, geometry of reactor, temperature of electrolytic solution and dynamic of the fluid in the cell. The experiments were carried on in order to find parameters for a stable abd steady operation. The choice for the electrolytic was silicate/alkali solution in various concentrations to operate in various voltage as well. Plasma was produced on negative (cathode) and positive (anode) electrode, in specific conditions. A stable operation on the cathode process was obtained with low concentration of the electrolytic in aqueous solution, current density around 250V effective voltage. For the evolution of plasma in anodic process it was required higher concentrations and higher... (Complete abstract click electronic access below)

Estudo da produção de hidrogênio eletrolítico a partir de fontes eólica, solar e hidrelétrica

Introduces technical, economic and environmentally competitive solutions in the energy market is a great challenge for society. This work examines each of these aspects considering the production of electrolytic hydrogen with energy from wind power, solar and hydropower, in order to ensure an overview of this energy carrier. Initially, an assessment of the technical aspects is made addressing existing electrolysers technologies, its main characteristics and differences. The geographical distribution of wind, solar and hydroelectric potential in Brazil is also mapped, and a configuration scheme of a hydrogen production system is discussed. Subsequently, the economic analysis calculates the cost of investment in the alkaline electrolyser of 60 Nm³ / h, similar to the Brazilian bus powered by hydrogen project, coordinated by EMTU. Since the main input of electrolysis is electricity, is analyzed the latest energy auctions of each primary source and it is calculated the cost of production of the wind, solar and hydropower hydrogen. Postponed to this, are investigated the intrinsic environmental impacts of electricity generation process, proposing a readjustment of an indicator of ecological efficiency for the production of hydrogen. Finally, the work discusses the concept of externalities and demonstrates how the incorporation of external costs can leverage the hydrogen economy. In short, it is evident that the wind and hydroelectric hydrogens are more promising compared to solar hydrogen, whether in the economic aspect, because it achieved lower costs, whether in the environmental aspect, because it reached the highest ecological efficiency

On-line monitoring of electrochemical degradation of paracetamol through a biomimetic sensor

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)