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Traditional occupational hygiene assessment of occupational exposures to organic gases and vapours rely on low flow (<200 ml/min) NIOSH sorbent tubes. This work investigates 3M charcoal filter media (JK50 and JK40, 3M, Inc.) for collection and analysis of organic vapours across 0.1-5 l/min. To enable this work, a custom exposure facility was constructed and validated within which organic analyte gas/vapour concentrations could be introduced at known concentrations while controlling environmental variables such as temperature and humidity and other variables. This facility enabled experiments designed to investigate collection and desorption efficiencies across a range of sample flow rates, temperature and humidity conditions for both NIOSH sorbent tubes (e.g. SKC tube) and 3M charcoal filter media. As a result of the investigations described in this thesis, the following conclusions are drawn. Performance of the 3M charcoal filter media for collection and desorption efficiencies for loading, storage time, humidity and breakthrough at low flow rates (<0.5 l/min) were found comparable to the SKC sorbent tube. It is concluded that 3M charcoal media (JK50 and JK40) are suitable for sampling and analyses of hydrocarbons at flow rates <0.5 l/min. The collection efficiencies of the 3M charcoal filter media were investigated at high flow rates (>0.5l/min) for the same parameters, i.e., loading, temperature and humidity. It is concluded that 3M charcoal filter media can be used with confidence in sampling and analysis of airborne hydrocarbons up to 5 l/min. The Wheeler-Jonas model was found to satisfactorily predict the adsorption kinetics of the 3M charcoal filter media at different loading values of hydrocarbons. It was therefore concluded that the model can be applied to determine the suitable amount of 3M charcoal filter media prior to sampling for a given loading.

Traditional occupational hygiene assessment of occupational exposures to organic gases and vapours rely on low flow (<200 ml/min) NIOSH sorbent tubes. This work investigates 3M charcoal filter media (JK50 and JK40, 3M, Inc.) for collection and analysis of organic vapours across 0.1 ¿ 5 l/min. To enable this work, a custom exposure facility was constructed and validated within which organic analyte gas/vapour concentrations could be introduced at known concentrations while controlling environmental variables such as temperature and humidity and other variables. This facility enabled experiments designed to investigate collection and desorption efficiencies across a range of sample flow rates, temperature and humidity conditions for both NIOSH sorbent tubes (e.g. SKC tube) and 3M charcoal filter media. As a result of the investigations described in this thesis, the following conclusions are drawn. Performance of the 3M charcoal filter media for collection and desorption efficiencies for loading, storage time, humidity and breakthrough at low flow rates (<0.5 l/min) were found comparable to the SKC sorbent tube. It is concluded that 3M charcoal media (JK50 and JK40) are suitable for sampling and analyses of hydrocarbons at flow rates <0.5 l/min. The collection efficiencies of the 3M charcoal filter media were investigated at high flow rates (>0.5l/min) for the same parameters, i.e., loading, temperature and humidity. It is concluded that 3M charcoal filter media can be used with confidence in sampling and analysis of airborne hydrocarbons up to 5 l/min. The Wheeler-Jonas model was found to satisfactorily predict the adsorption kinetics of the 3M charcoal filter media at different loading values of hydrocarbons. It was therefore concluded that the model can be applied to determine the suitable amount of 3M charcoal filter media prior to sampling for a given loading.

Ce travail de thèse porte sur l'élaboration et la caractérisation de jonctions tunnel magnétiques (JTM) polycristallines à barrière d'oxyde de titane de strontium, SrTiO3, qui se situe parmi les nouvelles barrières tunnel aux bandes interdites les plus étroites, recensées par la littérature. De telles barrières pourraient répondre à un besoin applicatif crucial : avoir un produit résistance x surface, RA, plus faible dans les JTM, ou à son corollaire, avoir une épaisseur de barrière plus forte à RA égal tout en conservant une magnétorésistance tunnel, TMR, élevée. De précédents travaux ont montré que le SrTiO3 présente une température de cristallisation inhabituellement basse (< 400°C) lorsqu'il est déposé par pulvérisation par faisceau d'ions (IBS) ce qui peut le rendre compatible avec les électrodes magnétiques standards constitutives des JTM. Le dépôt par IBS restant une technique pour le moins exotique au regard de l'état de l'art des JTM, nous avons dans un premier temps élaboré des JTM à barrière d'oxyde de magnésium, MgO, matériau phare de la spintronique. Cette étude a permis de mettre en avant les paramètres spécifiques à cette technique de dépôt influant sur les propriétés de transport des JTM, notamment le type d'oxydation. Dans un second temps, nous avons réalisé des JTM CoFeB/SrTiO3/CoFeB par IBS à partir d'une cible céramique de SrTiO3, en nous inspirant du travail effectué sur le MgO. Les influences de plusieurs paramètres de dépôt, d'oxydation et de recuit ont été analysées, conduisant à deux tendances opposées avec des systèmes présentant soit à une TMR élevée (18 %), soit un RA faible (2.6 Ohm.µm²). Des JTM SrTiO3 ont ensuite été nanostructurées pour la première fois et les tests électriques ont montré que les JTM ayant un bas RA présentaient un comportement ohmique alors que celles ayant une TMR élevée présentaient le comportement tunnel attendu. De plus, ces dernières présentent un claquage diélectrique intrinsèque à l'oxyde. En parallèle, des études microstructurales ont montré une qualité morphologique des JTM SrTiO3 semblable à celle des JTM MgO à l'état de l'art. Toutefois, ces observations n'ont pas permis de statuer sur le caractère cristallisé ou non des barrières en SrTiO3. Plusieurs pistes visant à déterminer la température de cristallisation du SrTiO3 dans la gamme des épaisseurs extraordinairement faibles des barrières tunnel ont été proposées. / This work is focused on the development and the characterization of polycrystalline magnetic tunnel junctions (MTJ) with strontium titanium oxide barrier, SrTiO3, identified as a low band gap tunnel barrier by literature. Such barrier could fulfill the critical application requirement: having a lower resistance area product (RA) in MTJ, or its corollary, having a thicker barrier at constant RA, while keeping the tunnel magnetoresistance ratio (TMR) high enough. Former studies have shown that SrTiO3 deposited by ion beam sputtering (IBS) could crystallize at an unusual low temperature (< 400°C) which could make it compatible with the magnetic layers of MTJs. In a first place, MTJs with a tunnel barrier made of a well known material in spintronics, namely MgO, were deposited. This preliminary work allowed us to highlight the specific parameters affecting the transport properties in MTJs deposited by IBS, including the oxidation type. In a second place, CoFeB/SrTiO3/CoFeB MTJs were developed using IBS and a SrTiO3 ceramic target, learning from our experience on MgO based MTJs. Many combinations of different parameters (including deposition, oxidation and annealing parameters) were explored, leading to two opposite tendencies with systems having either a high TMR (up to 18 %) or a low RA (down to 2.6 Ohm.µm²). SrTiO3 based MTJs were then patterned for the first time and submitted to electrical tests. These tests showed that the MTJs having a low RA exhibited an ohmic behaviour while the MTJs having a large TMR showed the expected tunnel characteristics. Furthermore, the latter MTJs showed an intrinsic dielectric breakdown. In parallel, microstructural characterizations have shown that SrTiO3 based MTJs and MgO based MTJ were alike morphologically. Nevertheless, these observations alone were not enough to assess on the crystalline state of SrTiO3. Many possibilities/tracks aiming at determining the crystallisation temperature of SrTiO3, in the range of extremely low thicknesses used in MTJs, are identified.

Thin-film transistors (TFTs) are primarily used as a switching element in liquid crystal displays. Currently, amorphous silicon is the dominant TFT technology for displays, but higher performance TFTs will become necessary to enable ultra-definition resolution high-frequency large-area displays. Amorphous zinc tin oxide (ZTO) TFTs were fabricated by RF magnetron sputter deposition. In this study, the effect of both deposition and post annealing conditions have been evaluated in regards to film structure, composition, surface contamination, and device performance. Both the variation of oxygen partial pressure during deposition and the temperature of the post-deposition annealing were found to have a significant impact on TFT properties. X-ray diffraction data indicated that the ZTO films remain amorphous even after annealing to 600° C. Rutherford backscattering spectrometry indicated that the Zn:Sn ratio of the films was ~1.7:1 which is slightly tin rich compared to the sputter target composition. X-ray photoelectron spectroscopy data indicated that the films had significant surface contamination and that the Zn:Sn ratios changed depending on sample annealing conditions. Electrical characterization of ZTO films using TFT test structures indicated that mobilities as high as 17 cm² V⁻¹ s⁻¹ could be obtained for depletion mode devices. It was determined that the electrical properties of ZTO films can be precisely controlled by varying the deposition conditions and annealing temperature. It was found that the ZTO electrical properties could be controlled where insulating, semiconducting and conducting films could be prepared. This precise control of electrical properties allowed us to incorporate sputter deposited ZTO films into resistive random access memory (RRAM) devices. RRAM are two terminal nonvolatile data memory devices that are very promising for the replacement of silicon-based Flash. These devices exhibited resistive switching between high-resistance states to low-resistance states and low-resistance states to high-resistance states depending on polarity of applied voltages and current compliance settings. The device switching was fundamentally related to the defect states and material properties of metal and insulator layers, and their interfaces in the metalinsulator-metal (MIM) structure. / Graduation date: 2012 / Access restricted to the OSU Community at author's request from Jan. 6, 2012 - Jan. 6, 2013

A buva (Conyza spp.) é uma planta daninha anual, comum em lavouras de soja da região Sul do Brasil, onde os herbicidas chlorimuron-ethyl e glyphosate são os mais utilizados para o seu controle. No entanto, nas últimas safras de soja observou-se controle insatisfatório desta planta daninha com esses herbicidas. Esse fato gerou a suspeita de seleção de biótipos resistentes. Assim, o objetivo da pesquisa foi avaliar a ocorrência de resistência múltipla aos herbicidas chlorimuron-ethyl e glyphosate em biótipos de buva. Na primeira etapa do trabalho, foram feitas coletas de sementes de buva em áreas com controle insatisfatório, totalizando 25 biótipos. Esses biótipos foram avaliados com relação à suscetibilidade e resistência ao chlorimuron e glyphosate, aplicando-se a máxima dose de registro desses herbicidas. Para segunda etapa do trabalho, foram selecionados 5 biótipos de buva com grau de suscetibilidade contrastante. Esses biótipos foram avaliados com curvas de dose-resposta e com 5 doses do herbicida chlorimuron-ethyl, aplicadas no estádio fenológico de 3 a 4 folhas. Na terceira etapa do trabalho, foi avaliada a resposta de 4 biótipos de buva aos herbicidas chlorimuron-ethyl, glyphosate e associação de chlorimuron-ethyl e glyphosate. Os herbicidas foram empregados em oito doses: 0,0; 6,25; 12,5; 25; 50; 100; 200 e 400, representadas em porcentagem da dose de 20 g ha-1 chlorimuron-ethyl, e de 720 g e.a. ha-1 glyphosate, aplicadas em três estádios de desenvolvimento (altura 0,5 a 1 cm e/ou 3 a 4 folhas; altura 1 a 2 cm e/ou 6 a 7 folhas e; altura 10 a 12 cm e/ou 12 a 14 folhas) dos biótipos de buva. Na última etapa do trabalho, avaliaram-se 15 herbicidas para controle alternativo da buva no estádio de desenvolvimento de 5 a 7 cm de altura e/ou 7 a 8 folhas. O trabalho foi conduzido na casa de vegetação, da Estação Experimental da Embrapa Trigo, em Passo Fundo/RS. Os resultados evidenciam que todos os biótipos são controlados com a dose de 20 g ha-1 de chlorimuronethyl, no estádio de desenvolvimento de 3 a 4 folhas. Contudo, observou-se susceptibilidade diferencial entre os biótipos em doses menores que 20 g ha-1 indicando resistência de nível baixo. Também, ficou evidente que os estádios de desenvolvimento dos biótipos de buva afetam significativamente a resposta destes aos herbicidas, sendo que quanto mais avançado o estádio menor a sensibilidade. A exceção foi o biótipo 5 que demonstrou resistência ao glyphosate, independentemente do estádio de desenvolvimento. Por fim, os tratamentos alternativos 2,4-D (1.042 g ha-1); amonium glufosinate (400 g ha-1); glyphosate (900 g e.a. ha- 1) + 2,4-D (1.042 g ha-1); glyphosate (900 g e.a ha-1) + amonium glufosinate (400 g ha-1); paraquat (600 g ha-1) + diuron (300 g ha-1); tembotrione (84 g ha-1) e tembotrione (84 g ha-1) + atrazine (1.000 g ha-1) controlaram, eficientemente, os biótipos de buva avaliados. Como conclusão, indica-se a aplicação do herbicida chlorimuron-ethyl nas doses máximas registradas, em estádios de desenvolvimentos da buva inferiores a cinco folhas, e que a prática de rotação de mecanismos de ação seja usada no manejo químico dessas áreas. / The horseweed (Conyza spp.) is an annual weed, common in soybean crops in southern Brazil, where the herbicide chlorimuron-ethyl and glyphosate are the most commonly used for its control. However, in recent soybean harvests it was observed unsatisfactory control of this weed with these herbicides. This fact originated suspicion of selection of resistant biotypes. The objective of the research was to evaluate the occurrence of multiple resistances to herbicides chlorimuron-ethyl and glyphosate in horseweed biotypes. In the first stage of the research, were collected horseweed seeds in areas with unsatisfactory control, totaling 25 biotypes. These biotypes were assessed for susceptibility and resistance to chlorimuron and glyphosate, applying the maximum dose of herbicide registration. In the second stage, were selected 5 horseweed biotypes with contrasting degree of susceptibility and evaluated dose-response curves, with 5 doses of the herbicide chlorimuron-ethyl applied at growth stage 3 - 4 leaves. In the third stage, we evaluated the response of four biotypes of horseweed to the herbicide chlorimuron-ethyl, glyphosate and association of chlorimuronethyl and glyphosate. Herbicides were applied in eight doses: 0.0, 6.25, 12.5, 25, 50, 100, 200 and 400, represented as a percentage of the dose of 20 g ha-1 chlorimuron-ethyl, and 720 g a.e. ha-1 glyphosate applied at three stages of development (height 0.5 - 1 cm and / or 3 - 4 leaves, height 1 - 2 cm, and / or 6 - 7 and leaves, height 10 - 12 cm and / or 12 - 14 leaves) biotypes of horseweed. In the last stage of the study, evaluated 15 alternative herbicides to control horseweed at stage 5 - 7 cm high and / or 7 - 8 leaves. The study was conducted in a greenhouse, at the Experimental Station of Embrapa Trigo, Passo Fundo / RS. The results show that all biotypes can be controlled with the dose of 20 g ha-1 chlorimuron-ethyl, at stage 3 - 4 leaves. However, it was observed differential susceptibility among biotypes at doses under than 20 g ha-1 indicating low resistance. It was also evident that the developmental stages of the biotypes of horseweed, significantly affect the response to these herbicides, whereas the more advanced the stage the lower sensitivity. The exception was the biotype 5 that show resistance to glyphosate, regardless of the stage of development. Finally, alternative treatments 2,4-D (1.042 g ha-1); ammonium glufosinate (400 g ha-1), glyphosate (900 g a.e. ha- 1) + 2,4-D (1.042 g ha-1), glyphosate (900 g a.e. ha-1) + ammonium glufosinate (400 g ha-1), paraquat (600 g ha-1) + diuron (300 g ha-1); tembotrione (84 g ha-1) and tembotrione (84 g ha- 1) + atrazine (1,000 g ha-1), effectively controlled the biotypes of horseweed evaluated. Conclusion indicates the application of herbicide chlorimuron-ethyl in maximum doses recorded in stadiums horseweed developments less than five leaves, and that the practice of rotating mechanisms of action are used in the chemical management of these areas.

A buva (Conyza spp.) é uma planta daninha anual, comum em lavouras de soja da região Sul do Brasil, onde os herbicidas chlorimuron-ethyl e glyphosate são os mais utilizados para o seu controle. No entanto, nas últimas safras de soja observou-se controle insatisfatório desta planta daninha com esses herbicidas. Esse fato gerou a suspeita de seleção de biótipos resistentes. Assim, o objetivo da pesquisa foi avaliar a ocorrência de resistência múltipla aos herbicidas chlorimuron-ethyl e glyphosate em biótipos de buva. Na primeira etapa do trabalho, foram feitas coletas de sementes de buva em áreas com controle insatisfatório, totalizando 25 biótipos. Esses biótipos foram avaliados com relação à suscetibilidade e resistência ao chlorimuron e glyphosate, aplicando-se a máxima dose de registro desses herbicidas. Para segunda etapa do trabalho, foram selecionados 5 biótipos de buva com grau de suscetibilidade contrastante. Esses biótipos foram avaliados com curvas de dose-resposta e com 5 doses do herbicida chlorimuron-ethyl, aplicadas no estádio fenológico de 3 a 4 folhas. Na terceira etapa do trabalho, foi avaliada a resposta de 4 biótipos de buva aos herbicidas chlorimuron-ethyl, glyphosate e associação de chlorimuron-ethyl e glyphosate. Os herbicidas foram empregados em oito doses: 0,0; 6,25; 12,5; 25; 50; 100; 200 e 400, representadas em porcentagem da dose de 20 g ha-1 chlorimuron-ethyl, e de 720 g e.a. ha-1 glyphosate, aplicadas em três estádios de desenvolvimento (altura 0,5 a 1 cm e/ou 3 a 4 folhas; altura 1 a 2 cm e/ou 6 a 7 folhas e; altura 10 a 12 cm e/ou 12 a 14 folhas) dos biótipos de buva. Na última etapa do trabalho, avaliaram-se 15 herbicidas para controle alternativo da buva no estádio de desenvolvimento de 5 a 7 cm de altura e/ou 7 a 8 folhas. O trabalho foi conduzido na casa de vegetação, da Estação Experimental da Embrapa Trigo, em Passo Fundo/RS. Os resultados evidenciam que todos os biótipos são controlados com a dose de 20 g ha-1 de chlorimuronethyl, no estádio de desenvolvimento de 3 a 4 folhas. Contudo, observou-se susceptibilidade diferencial entre os biótipos em doses menores que 20 g ha-1 indicando resistência de nível baixo. Também, ficou evidente que os estádios de desenvolvimento dos biótipos de buva afetam significativamente a resposta destes aos herbicidas, sendo que quanto mais avançado o estádio menor a sensibilidade. A exceção foi o biótipo 5 que demonstrou resistência ao glyphosate, independentemente do estádio de desenvolvimento. Por fim, os tratamentos alternativos 2,4-D (1.042 g ha-1); amonium glufosinate (400 g ha-1); glyphosate (900 g e.a. ha- 1) + 2,4-D (1.042 g ha-1); glyphosate (900 g e.a ha-1) + amonium glufosinate (400 g ha-1); paraquat (600 g ha-1) + diuron (300 g ha-1); tembotrione (84 g ha-1) e tembotrione (84 g ha-1) + atrazine (1.000 g ha-1) controlaram, eficientemente, os biótipos de buva avaliados. Como conclusão, indica-se a aplicação do herbicida chlorimuron-ethyl nas doses máximas registradas, em estádios de desenvolvimentos da buva inferiores a cinco folhas, e que a prática de rotação de mecanismos de ação seja usada no manejo químico dessas áreas. / The horseweed (Conyza spp.) is an annual weed, common in soybean crops in southern Brazil, where the herbicide chlorimuron-ethyl and glyphosate are the most commonly used for its control. However, in recent soybean harvests it was observed unsatisfactory control of this weed with these herbicides. This fact originated suspicion of selection of resistant biotypes. The objective of the research was to evaluate the occurrence of multiple resistances to herbicides chlorimuron-ethyl and glyphosate in horseweed biotypes. In the first stage of the research, were collected horseweed seeds in areas with unsatisfactory control, totaling 25 biotypes. These biotypes were assessed for susceptibility and resistance to chlorimuron and glyphosate, applying the maximum dose of herbicide registration. In the second stage, were selected 5 horseweed biotypes with contrasting degree of susceptibility and evaluated dose-response curves, with 5 doses of the herbicide chlorimuron-ethyl applied at growth stage 3 - 4 leaves. In the third stage, we evaluated the response of four biotypes of horseweed to the herbicide chlorimuron-ethyl, glyphosate and association of chlorimuronethyl and glyphosate. Herbicides were applied in eight doses: 0.0, 6.25, 12.5, 25, 50, 100, 200 and 400, represented as a percentage of the dose of 20 g ha-1 chlorimuron-ethyl, and 720 g a.e. ha-1 glyphosate applied at three stages of development (height 0.5 - 1 cm and / or 3 - 4 leaves, height 1 - 2 cm, and / or 6 - 7 and leaves, height 10 - 12 cm and / or 12 - 14 leaves) biotypes of horseweed. In the last stage of the study, evaluated 15 alternative herbicides to control horseweed at stage 5 - 7 cm high and / or 7 - 8 leaves. The study was conducted in a greenhouse, at the Experimental Station of Embrapa Trigo, Passo Fundo / RS. The results show that all biotypes can be controlled with the dose of 20 g ha-1 chlorimuron-ethyl, at stage 3 - 4 leaves. However, it was observed differential susceptibility among biotypes at doses under than 20 g ha-1 indicating low resistance. It was also evident that the developmental stages of the biotypes of horseweed, significantly affect the response to these herbicides, whereas the more advanced the stage the lower sensitivity. The exception was the biotype 5 that show resistance to glyphosate, regardless of the stage of development. Finally, alternative treatments 2,4-D (1.042 g ha-1); ammonium glufosinate (400 g ha-1), glyphosate (900 g a.e. ha- 1) + 2,4-D (1.042 g ha-1), glyphosate (900 g a.e. ha-1) + ammonium glufosinate (400 g ha-1), paraquat (600 g ha-1) + diuron (300 g ha-1); tembotrione (84 g ha-1) and tembotrione (84 g ha- 1) + atrazine (1,000 g ha-1), effectively controlled the biotypes of horseweed evaluated. Conclusion indicates the application of herbicide chlorimuron-ethyl in maximum doses recorded in stadiums horseweed developments less than five leaves, and that the practice of rotating mechanisms of action are used in the chemical management of these areas.