Made available in DSpace on 2014-12-17T14:07:06Z (GMT). No. of bitstreams: 1 JulioCPB_TESE.pdf: 3654750 bytes, checksum: 7f67c8015c3dc4175f16964a07eacd69 (MD5) Previous issue date: 2011-04-29 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Plasma diagnostics by Optical Emission Spectroscopy were performed for electrical discharge in three gas mixture respecting the combinations z N2 y Ar x H2, z N2 y Ar x O2 e z N2 y Ar x CH4, in which the indexes z and y systematically vary from 1 to 4 and x varies from 0 to 4, every one has dimension SCCM, resulting in 80 combinations. From the all obtained spectrums, the species CH (387,1 nm), N2+ (391,4 nm), Hβ (486,1 nm), Hα (656,3 nm), Ar (750,4 nm), O (777,4 nm) e O (842,6 nm) were analyzed because of their abundance and importance on the kinetic of reaction from the plasma to surface, besides their high dependences on the gases flows. Particularly interesting z, y and x combinations were chosen in order to study the influence of active species on the surface modification during the thermochemical treatment. From the mixtures N2 Ar O2 e N2 Ar CH4 were chosen three peculiar proportions which presented luminous intensity profile with unexpected maximum or minimum values, denominated as plasma anomaly. Those plasma concentrations were utilized as atmosphere of titanium treatment maintaining constant the control parameters pressure and temperature. It has been verified a relation among luminous intensity associated to N2+ and roughness, nanohardness and O atoms diffusion into the crystalline lattice of treated titanium and it has been seen which those properties becomes more intense precisely in the higher points found in the optical profile associated to the N2+ specie. Those parameters were verified for the mixture which involved O2 gas. For the mixture which involves CH4 gas, the relation was determinate by roughness, number of nitrogen and carbon atoms diffused into the titanium structure which presented direct proportionality with the luminous intensity referent to the N2+ and CH. It has been yet studied the formation of TiCN phases on the surface which presented to be essentially directly proportional to the increasing of the CH specie and inversely proportional to the increasing of the specie N2+ / Diagn?sticos de plasma por Espectroscopia de Emiss?o ?ptica foram realizados para descarga el?trica em tr?s misturas gasosas, dentro das seguintes combina??es: z N2 y Ar x H2, z N2 y Ar x O2 e z N2 y Ar x CH4, com os ?ndices z e y variando sistematicamente de 1 a 4 e x de 0 a 4, todos com dimens?o de SCCM, resultando em 80 combina??es. Dos espectros obtidos, foram analisadas as esp?cies CH (387,1 nm), N2+ (391,4 nm), Hβ (486,1 nm), Hα (656,3 nm), Ar (750,4 nm), O (777,4 nm) e O (842,6 nm) por serem mais abundantes e importantes na cin?tica de rea??o do plasma ? superf?cie, al?m de suas altas depend?ncias dos fluxos de g?s. Foram escolhidas combina??es z, y e x, particularmente interessantes para estudar a influ?ncia das esp?cies ativas na modifica??o da superf?cie durante o tratamento termoqu?mico. Das misturas N2 Ar O2 e N2 Ar CH4 foram escolhidas tr?s propor??es peculiares que apresentavam perfis de intensidade luminescente com m?ximos ou m?nimos inesperados classificados aqui como anomalias de plasma. Essas concentra??es de plasma foram utilizadas como atmosfera de tratamento de amostras de tit?nio, mantendo-se constante os par?metros press?o e temperatura. Verificou-se rela??o entre intensidade luminosa associada ? esp?cie N2+ e a rugosidade, nanodureza e a difus?o do oxig?nio na rede cristalina do tit?nio tratado e viu-se que essas propriedades se intensificam precisamente nos pontos de m?ximo encontrados no perfil ?ptico dessa esp?cie. Esses par?metros foram verificados para mistura que envolvia o g?s O2. Para a mistura em que se fez presente o g?s CH4, a rela??o foi determinada por meio da rugosidade, n?mero de ?tomos de nitrog?nio e carbono difundidos no tit?nio, que apresentou proporcionalidade direta com a intensidade luminosa referente ?s esp?cies N2+ e CH. Ainda foi estudada a forma??o de fases TiCN na sua superf?cie, que essencialmente se mostra diretamente proporcional ao crescimento da esp?cie CH e inversamente proporcional ao crescimento da esp?cie N2+

Les mémoires résistives PCRAM sont basées sur le passage rapide et réversible entre un état amorphe hautement résistif et un état cristallin faiblement résistif d’un matériau à changement de phase (PCM). Ces mémoires constituent un des candidats les plus prometteurs pour la nouvelle génération de mémoires non-volatiles grâce à un large éventail de propriétés uniques comme une vitesse de fonctionnement élevée, une capacité de stockage multi-niveaux sur plusieurs bits, une bonne endurance et une possibilité de miniaturisation poussée. Cependant, la nécessité d’utiliser des courants d’effacement (IRESET) importants pour l’étape d’amorphisation du PCM représente l’un des principaux freins à l’explosion de la technologie PCRAM sur le marché des mémoires non volatiles. Dans ce contexte, il a été démontré que le confinement du PCM dans des structures possédant des facteurs de forme élevés permet d’améliorer l’efficacité du chauffage nécessaire au changement de phase du PCM et donc de réduire les courants d’amorphisation. Afin d’incorporer des matériaux PCM dans de telles structures, il est alors nécessaire de développer un procédé de dépôt très conforme. C’est pourquoi un procédé de dépôt PE-MOCVD (Plasma Enhanced- Metal Organic Chemical Vapor deposition) à injection liquide pulsée a été développé dans ce travail. Dans un premier temps des films amorphes et homogènes du composé binaire GeTe ont été déposés à partir des précurseurs organométalliques TDMAGe et DIPTe. Les analyses XPS révèlent que les couches de GeTe déposées sont stoechiométriques mais présentent une forte contamination en carbone. Ainsi, un des objectifs de cette thèse a été de réduire le taux de carbone dans les couches afin d’optimiser leurs propriétés de changement de phase. Une étude de l’impact des paramètres de dépôt tel que la puissance, la pression, la nature et le débit des gaz utilisés est alors présentée. En étudiant et en optimisant les paramètres de dépôt, des couches de GeTe contenant seulement 2 % at. de carbone ont pu être obtenues. Dans un second temps, des films du composé ternaire GeSbTe ont été déposés en injectant simultanément les trois précurseurs TDMAGe, TDMASb et DIPTe dans le plasma de dépôt. Une large gamme de composition peut alors être obtenue en variant les paramètres d’injection et de dépôt. L’un des principaux avantages de ce procédé est la capacité de couvrir une large gamme de compositions permettant d’obtenir des films possédant des propriétés de changement de phase très variées. L’impact des paramètres plasma sur la conformité du dépôt a aussi été étudié. Il est montré que l’ajout d’une composante BF à la puissance RF du plasma permet d’améliorer le remplissage des structures possédant des facteurs de forme élevés. Enfin, l’intégration dans des dispositifs mémoires PCRAM tests de matériaux PCM obtenus par ce procédé PE-MOCVD a mis en évidence des propriétés électriques proches de celles obtenues avec des matériaux déposés par les procédés de dépôt conventionnels de type PVD. / Phase change random access memories PCRAM are based on the fast and reversible switch between the high resistive amorphous state and the low resistive crystalline state of a phase change material (PCM). These memories are considered to be one of the most promising candidates for the next generation of non volatile memories thanks to their unique set of features such as fast programming speed, multi-level storage capability, good endurance and high scalability. However, high power consumption during the RESET operation (IRESET) is the main challenge that PCRAM has to face in order to explode the non volatile memory market. In this context, it has been demonstrated that by integrating the phase change material (PCM) in high aspect ratio lithographic structures, the heating efficiency is improved leading to a reduced reset current. In order to fill such confined structures with the phase change material, a highly conformal deposition process is required. Therefore, a pulsed liquid injection Plasma Enhanced-Metal Organic Chemical Vapor Deposition process (PE-MOCVD) was developed in this work. First, amorphous and homogeneous GeTe films were deposited using the organometallic precursors TDMAGe and DIPTe as Ge and Te precursors. XPS measurements revealed a stoichiometric composition of GeTe but with high carbon contamination. Thus, one of the objectives of this work was to reduce the carbon contamination and to optimize the phase change properties of the deposited PCMs. The effect of deposition parameters such as plasma power, pressure and gas rate on the carbon contamination is then presented. By tuning and optimizing deposition parameters, GeTe films with carbon level as low at 2 at. % were obtained. Thereafter, homogeneous films of GeSbTe were deposited by injecting simultaneously the organometallic precursors TDMAGe, TDMASb and DiPTe in the plasma. A wide range of compositions was obtained by varying the injection and deposition operating parameters. Indeed, one of the main advantages of this process is the ability of varying films composition, which results in varying phase change characteristics of the deposited PCM. The impact of plasma parameters on the conformity of the process was also studied. It was shown that by adding a low frequency power component to the radio frequency power of the plasma, structures with high aspect ratio were successfully filled with the phase change material. Finally, electrical characterization of PCRAM test devices integrating phase change materials deposited by PE-MOCVD as active material have presented electrical properties similar to the ones obtained for materials deposited by conventional physical vapor deposition (PVD) process.

Magister Scientiae - MSc (Biotechnology) / Soybean have been listed as a priority commodity crop in South Africa (SA) and provide a good source of protein to the population. Therefore, soybean has been earmarked as an important food security crop and strategies are currently being discussed at governmental level to increase and sustain soybean production. However, the SA landscape poses many challenges to the agricultural sector such as prolong drought periods, flooding, nutrient poor soils, saline soils and heavy metal contaminated soils. Heavy metal (HM) contamination is becoming a serious concern and is aggravated by historical mining in SA. Indeed, SA has established itself as the number one ranked mining country in the world and is frequently mining metals such as chromium, vanadium, gold, zirconium, platinum, and antimony. Prolong rainfall near mining areas leads to acid mine drainage which lowers the soil pH to approximately two. These highly acidic soils will solubilize the metals and cause the metals to leach into river systems as well as the water table leading to increase heavy metal contamination in nearby soil sites. This increase metal content negatively affects seed germination and overall plant development. Nonetheless, plants have evolved numerous internal mechanisms that help them to survive HM toxicity; by either avoiding or tolerating the stress. Two stress-activated pathways that help the plant tolerate stress have attracted much interest i.e. the glyoxalase system and reactive oxygen species (ROS) - antioxidant system as they detoxify methylglyoxal (MG) and ROS. / 2021-08-31

Submitted by Daniel Araujo Gonçalves null (daniel.araujogoncalves@gmail.com) on 2016-08-01T13:43:54Z No. of bitstreams: 1 Goncalves_Tese_versão_final.pdf: 3648542 bytes, checksum: 7acd793a874f48c8a008a28e1e550948 (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-08-02T19:00:04Z (GMT) No. of bitstreams: 1 goncalves_da_dr_ilha.pdf: 3648542 bytes, checksum: 7acd793a874f48c8a008a28e1e550948 (MD5) / Made available in DSpace on 2016-08-02T19:00:04Z (GMT). No. of bitstreams: 1 goncalves_da_dr_ilha.pdf: 3648542 bytes, checksum: 7acd793a874f48c8a008a28e1e550948 (MD5) Previous issue date: 2016-07-08 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho foram desenvolvidos quatro métodos analíticos visando a determinação de elementos químicos em diversas amostras. O primeiro estudo consistiu na determinação de Cr e Mn em placentônios provenientes de bovinos por espectrometria de emissão atômica em filamento de tungstênio (WC AES). O tempo de integração de sinal para 30 ms, proporcionou LOD 45 vezes menor para Mn e 150 vezes menor para Cr com relação a 500 ms. Testes de adição e recuperação apresentaram desvio padrão (SD) de ± 0,02 mg L-1 e recuperações de 91 a 102%. No segundo foram realizadas quantificações de Cr em cápsulas medicinais produzidas na China, a WC AES. A faixa linear de trabalho para determinação de Cr por WC AES foi de 10-100 μg L-1. Os limites de detecção foram de 3 μg L-1, o que possibilitou determinações em um nível 28 vezes menor que o valor máximo de Cr recomendado em medicamentos pela Farmacopeia Americana (USP). A precisão (% RSD) foi calculada na faixa de 5,2 – 7,4% e não foram significativamente diferentes através da aplicação de um teste ANOVA fator único a nível de confiança de 95% (p > 0,05) quando comparados com a técnica de Espectrometria de emissão óptica com plasma acoplado indutivamente (ICP OES). No terceiro estudo, um Espectrometro de Emissão Óptica com plasma induzido por micro-ondas – MIP OES (MP-AES, Agilent 4200), foi usado em combinação com o método de análise por diluição de padrão (SDA) para determinar Al, Cr, Co, Cu, Fe, Mn, Ni e Zn em amostras de café, chá verde, energético, cerveja, whiskey e cachaça. Não foi necessária preparação da amostra, a não ser uma simples diluição em HNO3 1% v v-1. A eficiência do SDA foi avaliada por experimentos de adição e recuperação e os resultados foram comparados com os métodos tradicionais de calibração externa (EC), o padrão interno (IS) e adição de padrão (AS). As recuperações médias por SDA para vários elementos avaliadas neste trabalho foram entre 90 e 99%. Para o método tradicional de adições padrão, por exemplo, as recuperações médias entre 101 e 122% foram obtidos para os mesmos analitos e amostras. No quarto estudo um MIP OES (MP-AES, Agilent 4200) foi utilizado para a determinação de Cd, Cr, Cu, Ni e Pb na matriz de óleo fusel onde emprega-se a calibração externa preparada em solução de 1% HNO3 e 1-propanol. Soluções contendo 5 e 50% da matriz v v-1 foram diluidas em 1-propanol e solução de óleo fúsel puro foram analisados. Não foram observados efeitos de matriz quando empregou-se a calibração com soluções de 1-propanol mesmo para determinações na amostra não diluída, com recuperações entre 90-109%. Os LODs para Cd, Cr, Cu, Ni e Pb em 1-propanol foram de 0,03; 0,009; 0,01; 0,007 e 0,04 mg L-1, respectivamente. O procedimento descrito para o MIP OES é uma abordagem simples, exata e precisa para rastrear análise de elementos de óleo fúsel. / In this work were developed four analytical methods for the determination of chemical elements in several samples. The first study consisted in determination of Cr and Mn in placenton from bovine animals by Atomic emission spectrometry in tungsten filament (WC AES). Signal integration time for 30 ms, provided LOD 45 times lower for Mn and 150 times lower for Cr with respect to 500 ms. Addition and recovery tests presented standard deviation (SD) of ± 0,02 mg L-1 and recoveries of 91 to 102%. In the second were carried out baseline measurements of Cr in medicinal capsule produced in China by WC AES. The linear range for determination of Cr by WC AES was 10 - 100 μg L-1 . The limits of detection were 3 μg L-1 , which allowed determinations in a level 28 times smaller than the maximum value of Cr recommended medicines for the U.S. Pharmacopeial Convention (USP). The precision (% RSD) was estimated in the range of 5,2 – 7,4% and were not significantly different by applying a test ANOVA single factor at the level of confidence 95% (p > 0,05) when compared with Optical emission spectrometry with inductively coupled plasma (ICP OES). In the third study, a Spectrometer of Optical Emission plasma induced by microwave – MIP OES (MP-AES, Agilent 4200), was used in combination with the method of analysis for standard dilution (SDA) to determine Al, Cr, Co, Cu, Fe, Mn, Ni e Zn in samples of coffee, green tea, energetic, beer, whiskey and cachaça brazilian. It didn't require sample preparation except a simple dilution in HNO3 1% v v-1 . The efficiency of the SDA was evaluated by experiments of addition and recovery, and the results were compared with the traditional methods of external calibration (EC), the internal standard (IS) and addition of default (AS). Average recoveries for SDA to various elements evaluated in this study were between 90 and 99%. For the traditional method of standard additions, for example, the average recoveries between 101 and 122% were obtained for the same analytes and samples. In the fourth study a MIP OES (MP-AES, Agilent 4200), was used for the determination of Cd, Cr, Cu, Ni e Pb in the array of fusel oil where is used the external calibration solution prepared 1% HNO3 and1-propanol. Solutions containing 5 and 50% of the matrix v v-1 were dissolved in 1-propanol and fusel oil pure solution were analyzed. Matrix effects were not observed when it was calibration with 1-propanol solutions even for undiluted sample determinations, with recoveries between 90 - 109%. The LODs for Cd, Cr, Cu, Ni and Pb in 1-propanol were of 0,03; 0,009; 0,01; 0,007 and 0,04 mg L-1 , respectively. The procedure described for MIP OES is a simple, accurate and precise approach to trace elements analysis of fusel oil. / CAPES PDSE: 99999.002566/ 2014-01

Orientador: Mirian Cristina dos Santos / Resumo: Neste trabalho foram desenvolvidos quatro métodos analíticos visando a determinação de elementos químicos em diversas amostras. O primeiro estudo consistiu na determinação de Cr e Mn em placentônios provenientes de bovinos por espectrometria de emissão atômica em filamento de tungstênio (WC AES). O tempo de integração de sinal para 30 ms, proporcionou LOD 45 vezes menor para Mn e 150 vezes menor para Cr com relação a 500 ms. Testes de adição e recuperação apresentaram desvio padrão (SD) de ± 0,02 mg L-1 e recuperações de 91 a 102%. No segundo foram realizadas quantificações de Cr em cápsulas medicinais produzidas na China, a WC AES. A faixa linear de trabalho para determinação de Cr por WC AES foi de 10-100 μg L-1. Os limites de detecção foram de 3 μg L-1, o que possibilitou determinações em um nível 28 vezes menor que o valor máximo de Cr recomendado em medicamentos pela Farmacopeia Americana (USP). A precisão (% RSD) foi calculada na faixa de 5,2 – 7,4% e não foram significativamente diferentes através da aplicação de um teste ANOVA fator único a nível de confiança de 95% (p > 0,05) quando comparados com a técnica de Espectrometria de emissão óptica com plasma acoplado indutivamente (ICP OES). No terceiro estudo, um Espectrometro de Emissão Óptica com plasma induzido por micro-ondas – MIP OES (MP-AES, Agilent 4200), foi usado em combinação com o método de análise por diluição de padrão (SDA) para determinar Al, Cr, Co, Cu, Fe, Mn, Ni e Zn em amostras de café, chá verde, ene... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this work were developed four analytical methods for the determination of chemical elements in several samples. The first study consisted in determination of Cr and Mn in placenton from bovine animals by Atomic emission spectrometry in tungsten filament (WC AES). Signal integration time for 30 ms, provided LOD 45 times lower for Mn and 150 times lower for Cr with respect to 500 ms. Addition and recovery tests presented standard deviation (SD) of ± 0,02 mg L-1 and recoveries of 91 to 102%. In the second were carried out baseline measurements of Cr in medicinal capsule produced in China by WC AES. The linear range for determination of Cr by WC AES was 10 - 100 μg L-1 . The limits of detection were 3 μg L-1 , which allowed determinations in a level 28 times smaller than the maximum value of Cr recommended medicines for the U.S. Pharmacopeial Convention (USP). The precision (% RSD) was estimated in the range of 5,2 – 7,4% and were not significantly different by applying a test ANOVA single factor at the level of confidence 95% (p > 0,05) when compared with Optical emission spectrometry with inductively coupled plasma (ICP OES). In the third study, a Spectrometer of Optical Emission plasma induced by microwave – MIP OES (MP-AES, Agilent 4200), was used in combination with the method of analysis for standard dilution (SDA) to determine Al, Cr, Co, Cu, Fe, Mn, Ni e Zn in samples of coffee, green tea, energetic, beer, whiskey and cachaça brazilian. It didn't require sample prepara... (Complete abstract click electronic access below) / Doutor

Made available in DSpace on 2014-12-17T14:58:21Z (GMT). No. of bitstreams: 1 BrunoFCS_DISSERT.pdf: 2467148 bytes, checksum: dcbe5eb64bfff65b0ce2132826b8fb43 (MD5) Previous issue date: 2013-07-05 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Plasma DC hollow cathode has been used for film deposition by sputtering with release of neutral atoms from the cathode. The DC Plasma Ar-H2 hollow cathode currently used in the industry has proven to be effective in cleaning surfaces and thin film deposition when compared to argon plasma. When we wish to avoid the effects of ion bombardment on the substrate discharge, it uses the post-discharge region. Were generated by discharge plasma of argon and hydrogen hollow cathode deposition of thin films of titanium on glass substrate. The optical emission spectroscopy was used for the post-discharge diagnosis. The films formed were analyzed by mechanical profilometry technique. It was observed that in the spectrum of the excitation lines of argon occurred species. There are variations in the rate of deposition of titanium on the glass substrate for different process parameters such as deposition time, distance and discharge working gases. It was noted an increase in intensity of the lines of argon compared with the lines of titanium. Deposition with argon and hydrogen in glass sample observed a higher rate deposition of titanium as more closer the sample was in the discharge / O Plasma DC de catodo oco vem sendo utilizado para a deposi??o de filmes atrav?s de sputtering com libera??o de ?tomos neutros do c?todo. O Plasma DC de Ar-H2 de catodo oco usado atualmente na ind?stria tem demonstrado ser eficiente na limpeza de superf?cies e deposi??o de filmes finos quando comparado ao plasma de arg?nio. Quando desejamos evitar os efeitos do bombardeamento i?nico da descarga no substrato, utiliza-se a regi?o de p?s-descarga. Geraram-se descargas por plasma de arg?nio e hidrog?nio em catodo oco para deposi??o de filmes finos de tit?nio em substrato de vidro. A espectroscopia de emiss?o ?tica foi empregada para o diagn?stico na p?s-descarga. Os filmes formados foram analisados atrav?s da t?cnica de perfilometria mec?nica. Observou-se que no espectro das linhas de arg?nio ocorreu excita??o de esp?cies. Verificaram-se varia??es para a taxa de deposi??o do tit?nio sobre o substrato de vidro para diferentes par?metros do processo como: tempo de deposi??o, dist?ncia da descarga e gases de trabalho. Contatou-se um aumento da intensidade das linhas de arg?nio quando comparadas com as linhas de tit?nio. Para deposi??o com Arg?nio e hidrog?nio em amostra de vidro observou uma maior taxa deposi??o de tit?nio quanto mais pr?xima a amostra se encontrava da descarga

Made available in DSpace on 2014-12-17T14:58:21Z (GMT). No. of bitstreams: 1 EdsonJCS_DISSERT.pdf: 1649413 bytes, checksum: 32339cc7487693336b6710eaa3e1c93c (MD5) Previous issue date: 2013-07-05 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Many applications require that the plasma discharge is produced apart from the surface to be processed, thus preventing damage caused by bombardment and/or plasma radiation. In the post-discharge regime in various applications thermally sensitive materials can be used. In this work, active species produced by discharge and post-discharge hollow cathode were diagnosed by optical emission spectroscopy and mass spectrometry. The discharge was produced with the gases Ar and Ar - N2 gas flow ranging from 1 to 6 cm3/min and electric current between 150 to 600 mA. It was estimated that the ion density inside the hollow cathode, with 2 mm diameter ranged between 7.71 and 14.1 x 1015 cm-3. It was observed that the gas flow and the electric current changes the emission intensity of Ar and N2 species. The major ionic species detected by quadrupole mass spectrometry were Ar+ and N2+. The ratio of optical emission intensities of N2(1 +)/Ar(811 nm) was related to the partial pressure of N2 after the hollow cathode discharge at low pressure / Muitas aplica??es de plasma exigem que a descarga seja produzida distante da superf?cie a ser processada, evitando assim danos causados pelo bombardeamento e/ou radia??o do plasma. Nesse regime de p?s-descarga v?rias aplica??es em materiais termicamente sens?veis podem ser utilizadas. Neste trabalho esp?cies ativas produzidas por descarga e p?s-descarga de catodo oco foram diagnosticadas por espectroscopia de emiss?o ?ptica e espectrometria de massa. A descarga foi produzida com os gases Ar e mistura Ar - N2 com fluxo de g?s variando de 1 a 6 cm3/min e corrente el?trica entre 150 a 600 mA. Estimou-se que a densidade de ?ons no interior do c?todo oco, com 2 mm de di?metro, variou entre 7,71 e 14,1 x 1015 cm-3. Observou-se que o fluxo de g?s e a corrente el?trica alteram a intensidade de emiss?o das esp?cies de Ar e N2. As principais esp?cies i?nicas detectadas por espectrometria de massa quadrupolar foram de Ar+ e N2+. A raz?o das intensidades de emiss?o ?tica de N2 (1 +)/Ar(811 nm) foi relacionada com a press?o parcial de N2 na p?s-descarga de c?todo oco em baixa press?o

Made available in DSpace on 2014-12-17T14:58:21Z (GMT). No. of bitstreams: 1 IvanAS_DISSERT.pdf: 2705711 bytes, checksum: 6ce27c30f3560c2a25149045f4d7bb71 (MD5) Previous issue date: 2013-06-21 / The plasma produced by Dielectric Barrier Discharge (DBD) is a promising technique for producing plasma in atmospheric pressure and has been highlighted in several areas, especially in biomedical and textile industry, this is due to the fact that the plasma generated by DBD not reaches high temperatures, enabling use it for thermally sensitive materials. But still it is necessary the development of research related to understanding of the chemical, physical and biological interaction between the non-thermal plasma at atmospheric pressure with cells, tissues, organs and organisms. This work proposes to develop equipment DBD and characterize it in order to obtain a better understanding of the process parameters of plasma production and how it behaves under the parameters adopted in the process, such as distance, frequency and voltage applied between electrodes. For this purpose two techniques were used to characterize distinct from each other. The first was the method of Lissajous figures, this technique is quite effective and accurately for complete electrical characterization equipment DBD. The second technique used was Optical Emission Spectroscopy (EEO) very effective tool for the diagnosis of plasma with it being possible to identify the excited species present in the plasma produced. Finally comparing the data obtained by the two techniques was possible to identify a set of parameters that optimize the production when combined DBD plasma atmosphere in the equipment was built precisely in this condition 0.5mm-15kV 600Hz, giving way for further work / O plasma produzido por Descarga em Barreira Diel?trica (DBD) ? uma promissora t?cnica de produ??o de plasma em press?o atmosf?rica e vem se destacando em diversas ?reas, principalmente na biom?dica e ind?stria t?xtil, isso se deve ao fato de que o plasma gerado por DBD n?o atinge grandes temperaturas, possibilitando utiliz?-lo em materiais termicamente sens?veis. Por?m, ainda faz-se necess?rio o desenvolvimento de pesquisas relacionadas ao dom?nio e compreens?o dos mecanismos qu?micos, f?sicos e biol?gicos da intera??o entre o plasma n?o t?rmico ? press?o atmosf?rica com c?lulas, tecidos, ?rg?os e microrganismos. O presente trabalho se prop?s a desenvolver um equipamento DBD e caracteriz?-lo para assim obter um maior conhecimento dos par?metros do processo de produ??o de plasma e de como este se comporta mediante os par?metros adotados no processo, tais como dist?ncia, frequ?ncia e voltagem aplicada entre eletrodos. Para este fim foram utilizadas duas t?cnicas de caracteriza??o bem distintas entre si. A primeira foi o m?todo das figuras de Lissajous, essa t?cnica ? bastante eficaz e precisa para uma completa caracteriza??o el?trica de equipamentos DBD. A segunda t?cnica usada foi Espectroscopia de Emiss?o ?ptica (EEO) uma ferramenta bastante eficaz para o diagn?stico de plasma sendo poss?vel com ela identificar as esp?cies excitadas presentes no plasma produzido. Por fim confrontando os dados obtidos mediante as duas t?cnicas foi poss?vel identificar um conjunto de par?metros que quando associados aperfei?oam a produ??o do plasma DBD atmosf?rico no equipamento constru?do isso ocorreu mais precisamente na condi??o 0,5mm-600Hz-15kV, dando rumo para trabalhos futuros

Ce travail s'intéresse aux effets mécaniques créés par les décharges de surface et à leur efficacité comme actionneur. Une géométrie particulière d'électrodes permet de créer de manière pulsée un filament linéaire de plasma et de le chauffer très rapidement par effet Joule (à raison de plusieurs Joules en moins d'une microseconde). Ce chauffage rapide entraîne la formation d'ondes de choc qui peuvent interagir avec l'écoulement ambiant.Nous étudions le comportement électrique de la décharge de surface afin d'évaluer l'énergie déposée dans le filament de plasma par effet Joule. Pour ce faire, nous réalisons une étude paramétrique sur la configuration du circuit et nous déterminons les principaux paramètres qui pilotent la dynamique de la décharge. Différents modèles de résistance sont utilisés dans un code de simulation du circuit électrique, et leurs prédictions du courant et du dépôt d'énergie sont confrontées aux mesures expérimentales.Des mesures spectroscopiques dans différentes configurations de circuit donnent accès à certaines propriétés de la décharge comme la densité électronique, qui atteint des valeurs de 2x1018 cm-3. Le rayon du canal est également mesuré par imagerie rapide. Les ondes de chocs créées par la décharge de surface sont visualisées en imagerie Schlieren pour plusieurs configurations de circuit. Ces ondes de chocs créent une impulsion proportionnelle à l'énergie déposée dans la décharge. Nos développons un modèle de choc pour décrire la trajectoire du choc et pour calculer l'impulsion communiquée par la décharge de surface. Le modèle est en bon accord avec les mesures expérimentales et la décharge de surface a une efficacité mécanique de 0.12mNs/J pour notre configuration d'étude. Nous terminons cette étude en comparant cet actionneur potentiel avec d'autres actionneurs courants et proposons plusieurs pistes pour de futurs travaux. / In this study, we investigate the mechanical effects generated by pulsed surface discharges and their efficiency as an actuator. Using a specific electrode configuration, it is possible to create a short-lived, pulsed, rectilinear plasma channel and to heat it up rapidly (several Joules in less than a microsecond) through Joule heating. This fast energy deposition causes the formation of shock waves that can then interact with the surrounding flow.We study the electrical behavior of the pulsed surface discharge to assess the energy deposited in the plasma channel through Joule heating. To do so, we perform a parametric study on the circuit configuration and identify the main parameters driving the discharge dynamics. Several resistance models are implemented in a numerical description of the electrical circuit and their predictions of the current and deposited energy are compared with experimental measurements.Spectroscopic measurements in different circuit configurations give access to some of the plasma properties such as the electron number density that can reach values up to 2x1018 cm-3. Fast imaging also gives insight into the plasma channel radius. The shock waves generated by the pulsed surface discharge in different circuit configurations are visualized through Schlieren imaging. These shock waves generate an impulse that increases linearly with the energy deposited in the discharge. We develop a shock model to describe the shock trajectory and to compute the impulse imparted by the pulsed surface discharge. The model is in good agreement with our measurements and the pulsed surface discharge is found to have a mechanical efficiency of 0.12 mNs/J for our setup configuration. We conclude this study by comparing the proposed pulsed surface discharge actuator with other common designs and offer some directions for future studies.

O objetivo deste trabalho foi o desenvolvimento de metodologia analítica versátil e rápida para a determinação de Cr, Mn e Ni em aços martensíticos e austeníticos, através do processo de dissolução química parcial em sistema de injeção em fluxo acoplado ao Espectrômetro de Emissão Ótica acoplado indutivamente (ICP-OES). O procedimento, também priorizou menor manipulação de amostra e consumo de reagentes. A solução extratora, HNO3 e HCI 7,0 mol L-1 e 6,0 mol L-1 respectivamente 1:1 v/v foi utilizada para a dissolução química parcial dos aços inoxidáveis. A quantificação dos metais dissolvidos foi feita utilizando-se o método da somatória, que relaciona a concentração de um elemento individual com a somatória dos elementos determinados, segundo a fórmula: i% = Ci /Ct x 100, onde Ci é a concentração do elemento i e Ct é a soma das concentrações de todos elementos determinados. Os resultados não apresentaram diferença significativa em um nível de confiança de 95% com os valores certificados das amostras de referência e com os valores da dissolução total assistida por microondas. O procedimento apresentou freqüência analítica de 20 determinações por hora. / The objective of this work was the development of a versatile and fast analytical methodology for the determination of Cr, Mn, and Ni in martensitic and austenitic steels, through on-line partial chemical dissolution using a flow injection system coupled to an ICP-OES. The procedure also aimed the smallest sample manipulation and reagents consumption. The extractor solution, 7.0 mol L-1 HNO3 and 6.0 mol L-1 HCI 1:1 v/v, was used to the on-line partial chemical dissolution of the stainless steels. The quantification of the dissolved metals was made using a method, that relate the concentration of an individual element with the sum of all elements concentrations, applying the formula: i% = Ci /Ct x 100, where Ci is the concentration of the element i and Ct is the sum of the concentration of all elements determined. No significant difference has been present by the results, at a confidence level of 95%, with the certified values of the reference materials and with the total dissolution values obtained by microwave - assisted sample pretreatment. The procedure presented analytic frequency of 20 determinations per hour.