Study of vanadium doped ZnO films prepared by dc reactive magnetron sputtering at different substrate temperatures

ZnO films doped with vanadium (ZnO:V) have been prepared by dc reactive magnetron sputtering technique at different substrate temperatures (RT–500 C). The effects of the substrate temperature on ZnO:V films properties have been studied. XRD measurements show that only ZnO polycrystalline structure has been obtained, no V2O5 or VO2 crystal phase can be observed. It has been found that the film prepared at low substrate temperature has a preferred orientation along the (002) direction. As the substrate temperature is increased, the (002) peak intensity decreases. When the substrate temperature reaches the 500 C, the film shows a random orientation. SEM measurements show a clear formation of the nano-grains in the sample surface when the substrate temperature is higher than 400 C. The optical properties of the films have been studied by measuring the specular transmittance. The refractive index has been calculated by fitting the transmittance spectra using OJL model combined with harmonic oscillator.

Minimização de odores em contentores de resíduos sólidos

Mestrado em Engenharia Química

Estudo electroquímico de compostos naturais e semicondutores com possível utilização em células foto voltaicas

As células foto voltaicas orgânicas ou células de Gräetzel (depois do seu descobridor) são aparelhos para a colecta de energia solar que utilizam um semicondutor inorgânico e uma molécula orgânica. Dita molécula orgânica é capaz de excitar-se na presença de radiação electromagnética e ceder esta energia através da doação de electrões a este semicondutor. Embora estas estruturas e o seu processo de fabrico sejam relativamente pouco onerosas, o aproveitamento da energia solar é ainda muito baixo. Para além desta deficiência, os corantes sintéticos sofrem de “bleaching” ou então são reduzidos ou oxidados facilmente quando não conseguem transferir a energia que foi absorvida ou quando é difícil voltar ao estado original por dificuldades no completamento de circulação de electrões. Neste trabalho pretende-se então estudar o comportamento de moléculas e misturas complexas de moléculas com capacidade para serem excitadas pela luz solar. Como a dita xcitação promove a transferência de um electrão, este processo será seguido pela técnica de Voltametria cíclica. Como substâncias absorventes de luz utilizaremos compostos naturais (principalmente flavonóides) puros, ou então na forma de complexos naturais extraídos de algumas plantas. Estas misturas de corantes serão extractos aquosos (infusões) de casca de laranja e limão assim como extractos de folhas de cerejeira, com o objectivo de proporcionar lternativas aos flavonóides utilizados neste estudo. A caracterização voltamétrica desta célula é feita em diferentes formas de iluminação. Sobre a célula assim formada faz-se incidir rimeiro luz de lâmpadas fluorescentes, depois luz ultra violeta e por fim sem qualquer tipo de luz incidente. Na base do fabrico da variante mais clássica destas células está o semicondutor óxido de itânio (TiO2), por ser uma substância muito comum e barata e com propriedades semicondutoras notáveis. Uma forma comum de melhorar a eficiência deste material é introduzir dopantes com o intuito de melhorar a eficiência do processo de transferência electrónica. Um segundo objectivo deste trabalho é o estudo de sistemas semicondutor/molécula foto activa. Semicondutores como ZnO, TiO2 e TiO2 dopado serão então estudados. O gels de TiO2 ou o TiO2 dopado serão depositados sobre lâminas de vidro comum, nas quais foi anteriormente depositado uma película de alumínio que serve de condutor (eléctrodo egativo). Uma outra variante será a utilização de óxido de zinco, um semicondutor de baixo custo que por sua vez vai ser depositado em lâminas de alumínio comercial. A nossa célula foto electroquímica será então formada por moléculas de corante, uma lâmina e um semicondutor (que funcionará como eléctrodo de trabalho), com ou sem electrólito/catalizador (solução de iodo/iodeto), e eléctrodos de referência de Ag/AgCl, e outro auxiliar de grafite. Um outro objectivo é fazer um pequeno estudo sobre influencia do catalisador I2/etilenodiamina no comportamento electroquímico da célula, de forma a poder utilizar o solvente (etilenodiamina) com menor volatilidade do que a água, que é empregada no par I2/I3.m A importância deste facto prende-se com a limitada vida destas células quando o electrólito/solvente é evaporado pelas altas temperaturas da radiação incidente.

Estudo de problemas de corrosão em cabos de aço zincado

As cablagens metálicas são aplicadas abundantemente na montagem dos automóveis, para accionamento de diversos dispositivos, tais como a abertura de portas, abertura da mala ou da tampa do motor, abertura do tampão do depósito de combustível, accionamento do travão de mão, etc. Nas cablagens metálicas utilizadas na indústria automóvel é comummente utilizado arame entrançado de aço zincado, o qual foi já estudado resistir à agressividade das condições em que habitualmente trabalham. No entanto, para que esta estabilidade de funcionamento exista, torna-se necessário que a qualidade do arame entrançado seja a mais adequada. O presente trabalho surgiu da necessidade de averiguar quais as razões que estariam por detrás do aparecimento de quantidades relativamente abundantes de Óxido de Zinco (ZnO) em cablagens metálicas utilizadas na indústria automóvel, poucas semanas depois do seu fabrico. O estudo foi levado a cabo com vista a satisfazer as necessidades de investigação deste problema por parte de uma empresa de cablagens metálicas instalada no nosso país, a FicoCables, estabelecendo quais as causas-raiz deste problema, com vista a poder evitálo no futuro. O trabalho foi concluído com sucesso, tendo-se averiguado que existiam lacunas graves de limpeza do cabo entre as operações de conformação do arame e de zincagem, com deposição de elementos potenciadores do Óxido de Zinco na interface, os quais viriam a revelar-se cruciais à posteriori, para a nucleação e desenvolvimento do Óxido de Zinco na superfície do cabo.

Iron oxide/gold core/shell nanomagnetic probes and CdS biolabels for amplified electrochemical immunosensing of Salmonella typhimurium

There is an imminent need for rapid methods to detect and determine pathogenic bacteria in food products as alternatives to the laborious and time-consuming culture procedures. In this work, an electrochemical immunoassay using iron/gold core/shell nanoparticles (Fe@Au) conjugated with anti-Salmonella antibodies was developed. The chemical synthesis and functionalization of magnetic and gold-coated magnetic nanoparticles is reported. Fe@Au nanoparticles were functionalized with different self-assembled monolayers and characterized using ultraviolet-visible spectrometry, transmission electron microscopy, and voltammetric techniques. The determination of Salmonella typhimurium, on screen-printed carbon electrodes, was performed by square-wave anodic stripping voltammetry through the use of CdS nanocrystals. The calibration curve was established between 1×101 and 1×106 cells/mL and the limit of detection was 13 cells/mL. The developed method showed that it is possible to determine the bacteria in milk at low concentrations and is suitable for the rapid (less than 1 h) and sensitive detection of S. typhimurium in real samples. Therefore, the developed methodology could contribute to the improvement of the quality control of food samples.

Reduced fluoresceinamine as a fluorescent sensor for nitric oxide

A new fluorescent sensor for nitric oxide (NO) is presented that is based on its reaction with a non fluorescent substance, reduced fluoresceinamine, producing the highly fluorescent fluoresceinamine. Using a portable homemade stabilized light source consisting of 450 nm LED and fiber optics to guide the light, the sensor responds linearly within seconds in the NO concentration range between about 10–750 µM with a limit of detection (LOD) of about 1 µM. The system generated precise intensity readings, with a relative standard deviation of less than 1%. The suitability of the sensor was assessed by monitoring the NO generated by either the nitrous acid decomposition reaction or from a NO-releasing compound. Using relatively high incubation times, the sensor also responds quantitatively to hydrogen peroxide and potassium superoxide, however, using transient signal measurements results in no interfering species.

Copper, nickel and zinc removal by peanut hulls: batch and column studies in mono, tri-component systems and with real effluent

The main goal of this research study was the removal of Cu(II), Ni(II) and Zn(II) from aqueous solutions using peanut hulls. This work was mainly focused on the following aspects: chemical characterization of the biosorbent, kinetic studies, study of the pH influence in mono-component systems, equilibrium isotherms and column studies, both in mono and tri-component systems, and with a real industrial effluent from the electroplating industry. The chemical characterization of peanut hulls showed a high cellulose (44.8%) and lignin (36.1%) content, which favours biosorption of metal cations. The kinetic studies performed indicate that most of the sorption occurs in the first 30 min for all systems. In general, a pseudo-second order kinetics was followed, both in mono and tri-component systems. The equilibrium isotherms were better described by Freundlich model in all systems. Peanut hulls showed higher affinity for copper than for nickel and zinc when they are both present. The pH value between 5 and 6 was the most favourable for all systems. The sorbent capacity in column was 0.028 and 0.025 mmol g-1 for copper, respectively in mono and tri-component systems. A decrease of capacity for copper (50%) was observed when dealing with the real effluent. The Yoon-Nelson, Thomas and Yan’s models were fitted to the experimental data, being the latter the best fit.

Nano-CF: a Coordination Framework for macro-programming in wireless sensor networks

Wireless Sensor Networks (WSN) are being used for a number of applications involving infrastructure monitoring, building energy monitoring and industrial sensing. The difficulty of programming individual sensor nodes and the associated overhead have encouraged researchers to design macro-programming systems which can help program the network as a whole or as a combination of subnets. Most of the current macro-programming schemes do not support multiple users seamlessly deploying diverse applications on the same shared sensor network. As WSNs are becoming more common, it is important to provide such support, since it enables higher-level optimizations such as code reuse, energy savings, and traffic reduction. In this paper, we propose a macro-programming framework called Nano-CF, which, in addition to supporting in-network programming, allows multiple applications written by different programmers to be executed simultaneously on a sensor networking infrastructure. This framework enables the use of a common sensing infrastructure for a number of applications without the users having to worrying about the applications already deployed on the network. The framework also supports timing constraints and resource reservations using the Nano-RK operating system. Nano- CF is efficient at improving WSN performance by (a) combining multiple user programs, (b) aggregating packets for data delivery, and (c) satisfying timing and energy specifications using Rate- Harmonized Scheduling. Using representative applications, we demonstrate that Nano-CF achieves 90% reduction in Source Lines-of-Code (SLoC) and 50% energy savings from aggregated data delivery.

Analysis of the nano-surface of a modified glassy carbon electrode by pseudo phase plane method

This paper presents the Pseudo phase plane (PPP) method for detecting the existence of a nanofilm on the nitroazobenzene-modified glassy carbon electrode (NAB-GC) system. This modified electrode systems and nitroazobenze-nanofilm were prepared by the electrochemical reduction of diazonium salt of NAB at the glassy carbon electrodes (GCE) in nonaqueous media. The IR spectra of the bare glassy carbon electrodes (GCE), the NAB-GC electrode system and the organic NAB film were recorded. The IR data of the bare GC, NAB-GC and NAB film were categorized into five series consisting of FILM1, GC-NAB1, GC1; FILM2, GC-NAB2, GC2; FILM3, GC-NAB3, GC3 and FILM4, GC-NAB4, GC4 respectively. The PPP approach was applied to each group of the data of unmodified and modified electrode systems with nanofilm. The results provided by PPP method show the existence of the NAB film on the modified GC electrode.

One-step preparation of optically transparent Ni-Fe oxide film electrocatalyst for oxygen evolution reaction

Optically transparent cocatalyst film materials is very desirable for improved photoelectrochemical (PEC)oxygen evolution reaction (OER) over light harvesting photoelectrodes which require the exciting light to irradiate through the cocatalyst side, i.e., front-side illumination. In view of the reaction overpotential at electrode/electrolyte interface, the OER electrocatalysts have been extensively used as cocatalysts for PEC water oxidation on photoanode. In this work, the feasibility of a one-step fabrication of the transparent thin film catalyst for efficient electrochemical OER is investigated. The Ni-Fe bimetal oxide films, 200 nm in thickness, are used for study. Using a reactive magnetron co-sputtering technique, transparent(> 50% in wavelength range 500-2000 nm) Ni-Fe oxide films with high electrocatalytic activities were successfully prepared at room temperature. Upon optimization, the as-prepared bimetal oxide film with atomic ratio of Fe/Ni = 3:7 demonstrates the lowest overpotential for the OER in aqueous KOH solution, as low as 329 mV at current density of 2 mA cm 2, which is 135 and 108 mV lower than that of as-sputtered FeOx and NiOx thin films, respectively. It appears that this fabrication strategy is very promising to deposit optically transparent cocatalyst films on photoabsorbers for efficient PEC water splitting.

Electrospun Polyaniline-Reduced Graphene Oxide Composite Nanofibers Based High Sensitive Ammonia Gas Sensor

Ammonia is an important gas in many power plants and industrial processes so its detection is of extreme importance in environmental monitoring and process control due to its high toxicity. Ammonia’s threshold limit is 25 ppm and the exposure time limit is 8 h, however exposure to 35 ppm is only secure for 10 min. In this work a brief introduction to ammonia aspects are presented, like its physical and chemical properties, the dangers in its manipulation, its ways of production and its sources. The application areas in which ammonia gas detection is important and needed are also referred: environmental gas analysis (e.g. intense farming), automotive-, chemical- and medical industries. In order to monitor ammonia gas in these different areas there are some requirements that must be attended. These requirements determine the choice of sensor and, therefore, several types of sensors with different characteristics were developed, like metal oxides, surface acoustic wave-, catalytic-, and optical sensors, indirect gas analyzers, and conducting polymers. All the sensors types are described, but more attention will be given to polyaniline (PANI), particularly to its characteristics, syntheses, chemical doping processes, deposition methods, transduction modes, and its adhesion to inorganic materials. Besides this, short descriptions of PANI nanostructures, the use of electrospinning in the formation of nanofibers/microfibers, and graphene and its characteristics are included. The created sensor is an instrument that tries to achieve a goal of the medical community in the control of the breath’s ammonia levels being an easy and non-invasive method for diagnostic of kidney malfunction and/or gastric ulcers. For that the device should be capable to detect different levels of ammonia gas concentrations. So, in the present work an ammonia gas sensor was developed using a conductive polymer composite which was immobilized on a carbon transducer surface. The experiments were targeted to ammonia measurements at ppb level. Ammonia gas measurements were carried out in the concentration range from 1 ppb to 500 ppb. A commercial substrate was used; screen-printed carbon electrodes. After adequate surface pre-treatment of the substrate, its electrodes were covered by a nanofibrous polymeric composite. The conducting polyaniline doped with sulfuric acid (H2SO4) was blended with reduced graphene oxide (RGO) obtained by wet chemical synthesis. This composite formed the basis for the formation of nanofibers by electrospinning. Nanofibers will increase the sensitivity of the sensing material. The electrospun PANI-RGO fibers were placed on the substrate and then dried at ambient temperature. Amperometric measurements were performed at different ammonia gas concentrations (1 to 500 ppb). The I-V characteristics were registered and some interfering gases were studied (NO2, ethanol, and acetone). The gas samples were prepared in a custom setup and were diluted with dry nitrogen gas. Electrospun nanofibers of PANI-RGO composite demonstrated an enhancement in NH3 gas detection when comparing with only electrospun PANI nanofibers. Was visible higher range of resistance at concentrations from 1 to 500 ppb. It was also observed that the sensor had stable, reproducible and recoverable properties. Moreover, it had better response and recovery times. The new sensing material of the developed sensor demonstrated to be a good candidate for ammonia gas determination.