The first part of the master thesis is focused on theoretical analysis of the problems of diagnostics of an electric arc physical properties. In the thesis there is shown identification of spectral lines in experimentally measured electric arc spectra. The thesis deals also with energy balance of the arc. Next part of thesis is aimed to theoretical analysis of effects of electric arc on construction materials of low voltage electric apparatuses. The main part of thesis is devoted to experimental measurement of arc radial temperature changes, measurement of cathode temperature and research of electrical arc effect on selected construction materials of low voltage apparatuses.

Atomic emission spectrometry (AES) with a plasma has proven to be an important method for the analysis of metallic and nonmetallic species in a variety of matrices. Not only is atomic spectrometry useful for accurate and sensitive quantitative analysis, but it can be used as a means of unambiguous qualitative determinations. The most common matrix for AES samples is liquid. Whether aqueous or organic in nature, the majority of samples are dissolved in some sort of solvent. Unfortunately, for most modes of sample introduction, a large portion of the solvent is simultaneously introduced to the plasma discharge along with the analyte species. The plasma is thus required not only to sufficiently excite the analyte, but also to desolvate and vaporize the solvent species. These processes tend to diminish the available energy of the plasma that is to be directed toward the analyte. The nature of the energy loss due to solvent loading is not well understood and is the topic of debate for different systems. It is the focus of this dissertation to determine the effect of solvent loading on the Highly Efficient Microwave Induced Plasma (HEMIP). The magnitude of solvent loading for Ar and He discharges using different sample introduction systems is determined. The solvent load is shown to have two separate constituents: aerosol and vapor. Each of these are shown to affect the plasma in different ways. Two different sample introduction systems are evaluated for their respective solvent loadings: a cooled pneumatic nebulizer / double pass spray chamber and an ultrasonic nebulization system. These systems are compared under their normal operating conditions and for the two plasma support gases. High solvent loads are shown to destabilize both the Ar and He microwave plasmas, decrease analytical sensitivity, and attenuate the energy of the plasma discharge. The conditions under which solvent loading is minimized do not have a significant effect on the operational characteristics of the sample introduction systems, but provide the optimal analytical sensitivity and limits of detection for the HEMIP. / Ph. D.

Requirements of high performing engine oil are today necessary since the development of new machinery with modern standardsis a cutting edge technology demanding highly optimized components. One way of increasing the lubricating properties of engineoil is through the addition of antioxidants. Antioxidants included in lubricants have a number of functions, one being buffering theinorganic acids sulphuric acid and nitric acid.A novel method expected to lower the hydrogen ion concentration in acidified engine oil was evaluated in this thesis. Thecapability of four different types of cation exchangers to serve as complements for buffering additives in heavy vehicle engineswas assessed. Two cation exchangers were weak and two were strong. The analysis techniques used to evaluate what effect thecation exchangers have on engine oil were standard test method ASTM D4739, for measurements of the total base number (TBN),and inductively coupled plasma – atomic emission spectroscopy (ICP-AES). With ASTM D4739 it was found that weak cationexchangers give positive results with respect to the ability to decrease the hydrogen ion concentration in acidified engine oil.However, after begin subjected to strong cation exchangers, ASTM D4739 indicated that the hydrogen ion concentration in theacidified engine oil remains the same or increases.With additional literature studies of a variety of cation exchangers currently on the market, further optimization of the cationexchanging material could likely be achieved. In addition, the preparation method used during the evaluation of the cationexchangers should be optimized to give more reliable results.

Graphite Furnace Atomic Absorption Spectroscopy (GFAA) and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) are two primary means of analyzing metals at the elemental level. Both techniques are widely accepted as tools for basic research. Each technique is performed differently and has its own distinct advantages as well as disadvantages. The choice of which technique to employ is determined by the needs of the analysis and the limitations of the instrumental technique.The idea to merge the two techniques was originallydeveloped by the research group of Dr. Michael W. Blades of the University of British Columbia, Vancouver, in 1989, who successfully demonstrated a "mini" plasma within a graphite furnace. The goal of the research was to design a device that would combine the advantages of both techniques and hopefully eliminate or minimize the unfavorable characteristics of each technique.The sustaining of a "mini" plasma has been demonstrated by this group. Although the end result was similar to that of Blades' group, the method of achieving the plasma was such that the "new" instrument could easily be mounted onto the furnace via a small Interface/Power Coupling device. The advantages of this system are: existing GFAA instruments can be used; modification of the furnace and RF supply is minimal; RF electronics can be remotely located; removal of the interface device is quickly achieved; and sample introduction, through the use of an autosampler, can be facilitated with small modification.Background spectra were acquired using helium, argon, and a mixture of argon/helium. It was found that all the plasmas have highly structured backgrounds and demonstrate the potential for many analysis regions. Two methods of sample introduction were used in acquiring the line emission of magnesium: injection through the sample inlet port to the furnace and end window injection. Inlet port injection suffers from a loss of sensitivity, when compared to end cap injection, but is more easily performed. / Department of Chemistry

Parmi les systèmes dédiés à l’analyse directe des solides, la vaporisation électrothermique occupe une place de choix. Elle offre plusieurs avantages. Le temps de préparation des échantillons est considérablement réduit. Il n’y a pas de dilution induite par la minéralisation et les risques de pertes ou de contaminations durant cette étape sont éliminés. Son principe de fonctionnement consiste à transformer, par chauffage, quelques milligrammes d’échantillon en un aérosol, qui est ensuite transporté dans un spectromètre d’émission atomique par plasma à couplage inductif, où la composition élémentaire est mesurée. Une première étude fondamentale a permis de mieux comprendre la dynamique de l’aérosol formé et de définir les meilleures conditions opératoires. L’utilisation de cette technique pour la détermination élémentaire dans les végétaux a présenté cependant des difficultés supplémentaires : difficulté d’étalonnage, effets de matrice et grandes variabilités sur les concentrations mesurées. L’utilisation d’un support de cellulose pour les solutions étalons a permis d’harmoniser les conditions de formation de l’aérosol pour l’échantillon et pour l’étalon, et d’obtenir ainsi des résultats justes. Les effets de matrices ont pu être considérablement réduits par une calcination préalable des échantillons. Le manque de précision des mesures, causée par le manque d’homogénéité des échantillons, a pu être limitée en de réduisant significativement la taille des particules solides. Ces résultats obtenus sur des poudres ont permis d’autres applications comme l’analyse d’échantillons entiers ou la cartographie de la composition chimique d’organes végétaux. / Among the systems dedicated to the direct analysis of the solids, electrothermal vaporization takes up a place of choice. It offers several advantages. The preparation time of the samples is considerably reduced. There is no dilution induced by the digestion and the risks of losses or contaminations during this stage are eliminated. Its functioning consists to convert, by heating, a few milligrams of sample into an aerosol which is then transported in an inductively coupled plasma atomic emission spectrometer, where the elemental composition of the sample is determinate. A first fundamental study allowed to better understand the dynamics of the formed aerosol and to define the best operating conditions. However, the use of this technique to determine the elemental composition of solid plant samples presented additional difficulties: difficulty of calibration, matrix effects and important imprecision on the measured concentrations. The use of a cellulose support for the standard solutions allowed to harmonize the formation of the aerosol between the sample and the standard, and to obtain accurate results. The matrix effects can be considerably reduced by a preliminary dry-ashing of the samples. The variability of measurements, caused by the lack of homogeneity of the samples, was limited by reducing significantly the size of the solid particles. These results, obtained on powders, allowed other applications as the analysis of whole plant samples or the imaging of the chemical composition of plant organs.

Submitted by Rosangela Silva (rosangela.silva3@unioeste.br) on 2017-08-30T14:53:20Z No. of bitstreams: 2 Ana Julia Penteado.pdf: 1485037 bytes, checksum: 723d1b3bedb90392ef459d2a4cedeca8 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-08-30T14:53:20Z (GMT). No. of bitstreams: 2 Ana Julia Penteado.pdf: 1485037 bytes, checksum: 723d1b3bedb90392ef459d2a4cedeca8 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-02-07 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Lithium carbonate is the main drug used to treat bipolar disorder. This medicine has a narrow therapeutic range and is usually used in a chronic way by the patients, generating the need for therapeutic monitoring by means of plasma lithium quantification. In addition, records of toxic effects from chronic medical use reinforce the need for a tool that assists in the treatment. Thus, a reliable methodology for the quantification of lithium and a therapeutic adjuvant emerge as a means to improve the quality of life of the patient. In our work, we used the flame atomic absorption spectrometer to validate the method for quantification of lithium and the results were satisfactory, because they complied with the required criteria, assuring the reliability of the method. In order to find a therapeutic adjuvant, N-acetylcysteine (NAC) was studied for presenting important characteristics against the toxic effects caused by lithium. In our results lithium presented toxic effects mainly inducing oxidative stress, while the coadministration of NAC reversed this effect in the liver, kidney and brain organs. The use of NAC as a therapeutic adjuvant has been shown to be promising, however, further studies need to be performed to better understand this relationship. / O carbonato de lítio é o principal medicamento utilizado no tratamento do transtorno bipolar. Este medicamento possuí estreita faixa terapêutica e geralmente é utilizado de forma crônica pelos pacientes, gerando a necessidade da monitorização terapêutica por meio da quantificação plasmática de lítio. Além disso, os registros de efeitos tóxicos decorrentes do uso medicinal crônico remetem a necessidade de uma ferramenta que auxilie no tratamento. Desta forma, uma metodologia confiável para a quantificação de lítio e um adjuvante terapêutico surgem como meios de melhorar a qualidade de vida do paciente. Em nosso trabalho, utilizamos o espectrômetro de absorção atômica de chama para validar um método para quantificação de lítio e os resultados foram satisfatórios, pois cumpriram os critérios exigidos, assegurando a confiabilidade do método. Com foco em buscar um adjuvante terapêutico, a N-acetilcisteína (NAC) foi estudada por apresentar características importantes contra os efeitos tóxicos causados pelo lítio. Em nossos resultados o lítio apresentou efeitos tóxicos principalmente induzindo o estresse oxidativo, enquanto que a coadministração de NAC reverteu esse efeito nos órgãos fígado, rim e cérebro. O uso da NAC como adjuvante terapêutico mostrou ser promissor, porém, mais estudos precisam ser realizados para entender melhor essa relação.

Entre os inibidores de corrosão clássicos que já são utilizados na indústria do petróleo, foram estudadas a imidazolina oleica e a quaternária através de técnicas eletroquímicas, gravimétrica e analíticas, para avaliar a eficiência de inibição e como esses inibidores atuam em meio ácido. O meio agressivo foi uma solução de NaCl 3,5% em massa acidificada com ácido clorídrico até atingir um pH=2 com o objetivo de simular o ambiente de extração petrolífera. O substrato empregado foi o aço carbono 1020. As técnicas eletroquímicas utilizadas foram: monitoramento do potencial de circuito aberto, medidas de resistência de polarização linear, espectroscopia de impedância eletroquímica (EIE ) e curvas de polarização. Os valores das componentes real e imaginária de impedância indicam uma resistência maior aos processos de transferência de carga com o aumento da concentração dos inibidores e os Diagramas de Bode de ângulo de fase, revelaram a presença de uma camada de inibidor adsorvida sobre o metal com uma constante de tempo em altas frequências observada para a imidazolina oleica e quaternária. Para a imidazolina quaternária, verificou-se que só para tempos maiores de imersão é que o filme se adsorve de forma eficiente demonstrando uma cinética mais lenta de adsorção. Nos ensaios gravimétricos, os resultados de taxa de corrosão em m/ano foram decrescentes com o tempo após período de imersão de 30 dias, para ambas as imidazolinas. O uso das técnicas analíticas foi necessário a fim de se compreender melhor o comportamento das imidazolinas sobre o aço no meio estudado. Os resultados da análise de íons férricos em solução, por emissão atômica, foram obtidos durante várias amostragens durante o período do ensaio de perda de massa, e foi possível verificar um processo de inibição da corrosão até doze dias de imersão do metal, depois disto ocorre um disparo na quantidade de ferro liberado em solução, sugerindo que pode estar ocorrendo uma degradação do inibidor após 12 dias de imersão. Para esclarecer esse ponto, análises por espectroscopia Raman dos produtos de fundo formados durante os ensaios de perda de massa indicaramm que a degradação pode realmente estar ocorrendo. Foi confirmado, também por espectroscopia Raman sobre a superfície do aço após imersão prévia em solução contendo a imidazolina oleica, que há uma película adsorvida que protege o metal do meio agressivo. Técnica de microscopia eletrônica de varredura foi utilizada para caracterizar os corpos de prova na ausência e presença do inibidor, depois dos ensaios eletroquímicos e foi possível caracterizar, através dessa técnica a maior eficiência inibidora do filme de imidazolina quaternária. Dois tipos de nanoconatiners foram avaliados para o encapsulamento das duas imidazolinas estudadas: nanocontainers a base do argilomineral haloiista e sílica mesoporosa tipo SBA 15. Resultados de impedância eletroquímica mostraram a liberação dos inibidores de corrosão encapsulados com o tempo de imersão. Análise na região do infravermelho por sonda de fibra ótica foi utilizada para comprovar química e qualitativamente a liberação do inibidor a partir dos nanorreservatórios, no meio agressivo. / Among the traditional corrosion inhibitors which are already used in Oil and Gas industry, it oleic and quaternary imidazolines have been studied with electrochemical, gravimetric and analytical techniques to assess the inhibition efficiency and the inhibiting action in acidic medium. The aggressive medium was a 3.5% w/w NaCl solution acidified with hydrochloric acid to pH = 2 in order to simulate oil extraction environment. The metallic substrate used was a mild carbon steel. The electrochemical techniques used were open circuit potential monitoring the, linear polarization measurements, electrochemical impedance spectroscopy (EIS) and polarization curves. The real and imaginary components values of impedance indicated greater resistance to charge transfer processes with increasing inhibitor concentration and phase angle Bode diagrams o showed the presence of adsorbed inhibitor on the metal surface with a time constant at high frequencies observed for oleic and quaternary imidazolines. For quaternary imidazoline, it was found that only after long time of immersion the film adsorbs effectively, showing slower adsorption kinetics. In weight loss tests, the corrosion rate results decreased with time for both inhibitors. The use of analytical techniques helped to have a better understanding of both imidazolines behavior. The analysis of ferric ions in the solution by atomic emission were obtained for several electrolyte samples withdrawn during weight lost test period; it was possible to verify a efficient corrosion inhibition of carbon steel till twelve days of immersion and after that an increase on the iron release to the solution occurs , suggesting that it might be experiencing inhibitor degradation after twelve days of immersion. To clarify this point, Raman spectroscopy analysis of the sediment formed during the weight loss tests was performed and the results indicated that the degradation may actually be occurring. It was confirmed also by Raman spectroscopy analysis performed on steel surface after previous immersion in solution containing oleic imidazoline, which has adsorbed as a film which protects the metal against aggressive medium. Scanning electron microscopy was used to characterize the substrate surface morphology in the absence and presence of inhibitors after electrochemical tests. The technique has proven the presence of a persistent adsorbed quaternary imidazoline film . Two types of nanoconatiners were evaluated: halloysite clay nanocontainers and SBA-15 mesoporous silica. Electrochemical evaluation of the release of the encapsulated corrosion inhibitors was proven. IR probe technique was used to confirm chemical and quantitatively the release of the encapsulated inhibitor in the electrolyte.

Obsidian has been a center of interest both for geologists and archaeologists. Geologists have studied on physical and chemical properties of obsidian where archaeologists have worked on this material as a common artifact found in excavations. In this study, obsidian samples from &Ccedil / atalh&ouml / y&uuml / k excavations are examined using their rare earth element (REE) concentrations. Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) have been used for this purpose. A mixture (4:1) of lithium metaborate and lithium tetraborate was used for fusion of samples. Because of the low concentrations of REEs, a preconcentration step is needed. Successful recovery results have been achieved with Amberlite IR-120. The developed method is tested using the standard reference material SARM-1.

Entre os inibidores de corrosão clássicos que já são utilizados na indústria do petróleo, foram estudadas a imidazolina oleica e a quaternária através de técnicas eletroquímicas, gravimétrica e analíticas, para avaliar a eficiência de inibição e como esses inibidores atuam em meio ácido. O meio agressivo foi uma solução de NaCl 3,5% em massa acidificada com ácido clorídrico até atingir um pH=2 com o objetivo de simular o ambiente de extração petrolífera. O substrato empregado foi o aço carbono 1020. As técnicas eletroquímicas utilizadas foram: monitoramento do potencial de circuito aberto, medidas de resistência de polarização linear, espectroscopia de impedância eletroquímica (EIE ) e curvas de polarização. Os valores das componentes real e imaginária de impedância indicam uma resistência maior aos processos de transferência de carga com o aumento da concentração dos inibidores e os Diagramas de Bode de ângulo de fase, revelaram a presença de uma camada de inibidor adsorvida sobre o metal com uma constante de tempo em altas frequências observada para a imidazolina oleica e quaternária. Para a imidazolina quaternária, verificou-se que só para tempos maiores de imersão é que o filme se adsorve de forma eficiente demonstrando uma cinética mais lenta de adsorção. Nos ensaios gravimétricos, os resultados de taxa de corrosão em m/ano foram decrescentes com o tempo após período de imersão de 30 dias, para ambas as imidazolinas. O uso das técnicas analíticas foi necessário a fim de se compreender melhor o comportamento das imidazolinas sobre o aço no meio estudado. Os resultados da análise de íons férricos em solução, por emissão atômica, foram obtidos durante várias amostragens durante o período do ensaio de perda de massa, e foi possível verificar um processo de inibição da corrosão até doze dias de imersão do metal, depois disto ocorre um disparo na quantidade de ferro liberado em solução, sugerindo que pode estar ocorrendo uma degradação do inibidor após 12 dias de imersão. Para esclarecer esse ponto, análises por espectroscopia Raman dos produtos de fundo formados durante os ensaios de perda de massa indicaramm que a degradação pode realmente estar ocorrendo. Foi confirmado, também por espectroscopia Raman sobre a superfície do aço após imersão prévia em solução contendo a imidazolina oleica, que há uma película adsorvida que protege o metal do meio agressivo. Técnica de microscopia eletrônica de varredura foi utilizada para caracterizar os corpos de prova na ausência e presença do inibidor, depois dos ensaios eletroquímicos e foi possível caracterizar, através dessa técnica a maior eficiência inibidora do filme de imidazolina quaternária. Dois tipos de nanoconatiners foram avaliados para o encapsulamento das duas imidazolinas estudadas: nanocontainers a base do argilomineral haloiista e sílica mesoporosa tipo SBA 15. Resultados de impedância eletroquímica mostraram a liberação dos inibidores de corrosão encapsulados com o tempo de imersão. Análise na região do infravermelho por sonda de fibra ótica foi utilizada para comprovar química e qualitativamente a liberação do inibidor a partir dos nanorreservatórios, no meio agressivo. / Among the traditional corrosion inhibitors which are already used in Oil and Gas industry, it oleic and quaternary imidazolines have been studied with electrochemical, gravimetric and analytical techniques to assess the inhibition efficiency and the inhibiting action in acidic medium. The aggressive medium was a 3.5% w/w NaCl solution acidified with hydrochloric acid to pH = 2 in order to simulate oil extraction environment. The metallic substrate used was a mild carbon steel. The electrochemical techniques used were open circuit potential monitoring the, linear polarization measurements, electrochemical impedance spectroscopy (EIS) and polarization curves. The real and imaginary components values of impedance indicated greater resistance to charge transfer processes with increasing inhibitor concentration and phase angle Bode diagrams o showed the presence of adsorbed inhibitor on the metal surface with a time constant at high frequencies observed for oleic and quaternary imidazolines. For quaternary imidazoline, it was found that only after long time of immersion the film adsorbs effectively, showing slower adsorption kinetics. In weight loss tests, the corrosion rate results decreased with time for both inhibitors. The use of analytical techniques helped to have a better understanding of both imidazolines behavior. The analysis of ferric ions in the solution by atomic emission were obtained for several electrolyte samples withdrawn during weight lost test period; it was possible to verify a efficient corrosion inhibition of carbon steel till twelve days of immersion and after that an increase on the iron release to the solution occurs , suggesting that it might be experiencing inhibitor degradation after twelve days of immersion. To clarify this point, Raman spectroscopy analysis of the sediment formed during the weight loss tests was performed and the results indicated that the degradation may actually be occurring. It was confirmed also by Raman spectroscopy analysis performed on steel surface after previous immersion in solution containing oleic imidazoline, which has adsorbed as a film which protects the metal against aggressive medium. Scanning electron microscopy was used to characterize the substrate surface morphology in the absence and presence of inhibitors after electrochemical tests. The technique has proven the presence of a persistent adsorbed quaternary imidazoline film . Two types of nanoconatiners were evaluated: halloysite clay nanocontainers and SBA-15 mesoporous silica. Electrochemical evaluation of the release of the encapsulated corrosion inhibitors was proven. IR probe technique was used to confirm chemical and quantitatively the release of the encapsulated inhibitor in the electrolyte.

Incineration is an attractive solution to the problems of disposing of municipal solid wastes and supplying energy. Because up to 25 percent of the waste in refuse-derived-fuel systems is ash, the physical and chemical characteristics of ash become more and more important for its potential impacts and methods suitable for their disposal. Trace elements concentration in ash is of great interest because of its relationship to regulatory criteria under the Resource Conservation and Recovery Act (RCRA) regarding toxicity and hazards. The applications of a microwave oven sample dissolution method has been tested on a variety of standard reference materials, with reproducible and accurate results. Fourteen trace elements, As, Ba, Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Se, Tl, V, and Zn, from the dissolved ash samples were determined by inductively coupled plasma atomic emission spectrometry.