Um dos métodos mais utilizados para proteção contra a corrosão de aços comuns consiste na proteção catódica com revestimentos metálicos eletroquimicamente mais ativos, que estes. Os revestimentos de zinco são os mais usados para este tipo de proteção. De forma a protegerem o substrato, estes revestimentos devem atuar como anodos de sacrifício, sofrendo corrosão e transformando o substrato de aço em catodo. Todavia, não é de interesse, que o revestimento de zinco apresente altas taxas de corrosão de forma que a proteção contra a corrosão conferida ao aço seja duradoura. Uma das formas mais empregadas para reduzir a velocidade de corrosão do revestimento de zinco é por meio de tratamentos da superfície, por exemplo, por tratamentos de conversão. Os tratamentos de conversão mais eficientes são os que utilizam e geram rejeitos, que contêm íons de cromo hexavalente. Todavia, estes íons são carcinogênicos e tóxicos e, dessa forma, os processos que os utilizam em alguma etapa do tratamento, vêm sofrendo crescentes restrições, já sendo proibidos em países com leis ambientais mais rígidas. Esta é a razão para o crescente interesse e grande investimento em pesquisa tratamentos, que possam resultar em revestimentos com potencialidade para substituir, de forma eficiente e efetiva o uso do cromo hexavalente. Este foi o objetivo do presente trabalho. Neste estudo, foi investigado o efeito de tratamentos, que resultam em camadas de conversão na presença de ácido oxálico e na proteção contra a corrosão da superfície do zinco. Camadas de conversão foram obtidas por imersão de amostras de zinco em soluções de ácido oxálico (ácido etanodióico) com diferentes concentrações. Todas as soluções de tratamento apresentaram elevada acidez e resultaram em ataque da superfície de zinco com formação de revestimento de conversão com diferentes características. Ensaios preliminares de névoa salina foram então realizados para investigar a proteção conferida pelo sistema revestimento de conversão-verniz contra a corrosão do substrato de zinco. Estes ensaios foram decisivos para a escolha da faixa de concentração do banho de conversão com maior potencial para formação de revestimentos de conversão protetores. Os resultados deste ensaio e os de espectroscopia de impedância eletroquímica mostraram que tratamentos em soluções com composição superiores a 10-1 M de ácido oxálico resultaram em camadas muito defeituosas, nas quais o ataque localizado do substrato metálico é favorecido, sendo obtidas impedâncias menores que a superfície do zinco sem qualquer tratamento. Os resultados de XPS mostraram, que os revestimentos de conversão formados em soluções de ácido oxálico na faixa de 10-3 M a 10-1 M são compostos de oxalato de zinco e produtos de corrosão do zinco, especificamente ZnO, Zn (OH)2, e ZnCO3. Já a concentração de 10-1 M de ácido oxálico foi a, que produziu os resultados mais promissores com a formação de um revestimento, que conferiu proteção mais duradoura à superfície do zinco entre os obtidos. As espessuras médias das camadas de conversão de oxalato de zinco formadas em soluções com 10-1 M e 1 M de ácido oxálico, estimadas por FIB, foram respectivamente 600 nm e 300 nm, o que mostra que a concentração de 1 M de ácido causou intenso ataque corrosivo da superfície, enquanto a camada formada em meio com 10-1 M permitiu a deposição de camada mais espessa e mais protetora contra a corrosão do substrato. Os resultados de XPS indicaram a degradação da camada de oxalato de zinco com o tempo de ensaio, porém o ataque desta ao longo do ensaio de corrosão, resulta na formação de simonkolleite, identificada por difração de raios X, para períodos mais longos do ensaio de corrosão, no caso do revestimento formado em solução com 10-1 M em comparação a 1M. A simonkolleite atua por efeito barreira bloqueando os defeitos/porosidade da camada. O crescente acúmulo destes produtos de corrosão com a continuidade do processo corrosivo e a aderência destes ao substrato metálico foi indicada para superfície tratada em solução com 10-1 M de ácido oxálico. Finalmente, foi proposto um modelo para interação entre o revestimento de conversão de oxalato de zinco e os produtos de corrosão em que a retenção dos produtos de corrosão na superfície faz com, que a camada na superfície se torne mais espessa e mais compacta com o tempo de exposição ao ensaio de corrosão. Estas observações explicam o aumento de impedância observado com o tempo de ensaio nesta condição. Os resultados obtidos permitiram concluir, que o revestimento de conversão de oxalato de zinco formado em solução com 10-1 M de ácido oxálico resulta em proteção efetiva do substrato metálico além de apresentar boa aderência com camada de verniz. Estes resultados indicam potencialidade deste tratamento como preparação de superfícies de zinco, que serão recobertas com revestimentos orgânicos (tintas, vernizes ou lacas). / One of the most used methods for protection of common steels is the cathodic protection by galvanic coupling with metallic coatings electrochemically more active than these. Zinc coatings are the most commonly used for this type of protection. In order to protect the metallic substrate, these coatings must act as sacrificial anodes, corroding themselves and converting the steel substrate into cathode. However, it is not appropriate that the zinc coating presents high corrosion rates, so that the corrosion protection conferred to the steel is long-lasting. One of the most commonly employed methods of reducing the corrosion rate of zinc coatings is by surface treatments, such as, conversion treatments. The most efficient conversion treatments to date are those that use hexavalent chromium ions or generate residues containing these ions. However, hexavalent chromium is carcinogenic and toxic and, therefore, the processes that involve their use at some stage of the treatment, are under increasing restrictions, and have already been prohibited in developed countries. This is the reason for the growing interest and great investment in research studies in search for treatments that may result in coatings with the potential to efficiently and effectively replace the use of hexavalent chromium. This was the objective of the present study. In this study, the effect of treatments in oxalic acid solutions that resulted in conversion layers on the corrosion protection of zinc surface has been investigated. Conversion layers were obtained by immersion of zinc samples in solutions of oxalic acid (ethanedioic acid) with different concentrations. All the treatment solutions presented high acidity and resulted in attack of zinc surface and formation of conversion coatings of different characteristics. A layer of varnish was applied and preliminary salt spray tests were then carried out to investigate the corrosion protection provided by the system conversion coating -varnish to the zinc substrate. These tests were decisive for the choice of the conversion bath composition range with greater potentialities for the formation of protective conversion coatings. The results of the salt spray test and of electrochemical impedance spectroscopy (EIS) showed that treatments in solutions with compositions greater than 10-1 M of oxalic acid resulted in very defective conversion layers in which the localized attack of the metallic substrate is favored, and lower impedances than the zinc surface without any treatment were obtained for surfaces treated in these solution. The XPS results showed that conversion coatings formed in oxalic acid solutions in the range of 10-3 M to 10-1 M are composed of zinc oxalate and zinc corrosion products, specifically ZnO, Zn (OH)2, and ZnCO3. The concentration related to the most promising results was 10-1 M and in this solution, the coating formed that promoted the longer lasting protection of the zinc surface among those obtained. The average thicknesses of the zinc oxalate conversion layers formed in solutions with 10-1 M and 1 M of oxalic acid, estimated by FIB, were respectively 600 nm and 300 nm. This result showed that in 1 M of oxalic acid an intense corrosive attack of the zinc surface occurred, while the layer formed in 10-1 M was thicker and more protective against substrate corrosion. The XPS results indicated degradation of the zinc oxalate layer formed in 10-1 M solution with time of exposure to the test solution, but for the protection of the coating lasted for longer periods, comparatively to that formed in 1M solution, once the attack of the first film resulted in formation of simonkolleite, which was identified by X-ray diffraction. Simonkolleite acts by barrier effect blocking defects / porosity in the conversion layer. The increasing accumulation of corrosion products with test time and their adhesion to the metallic substrate was indicated for surface treated in solution with 10-1 M of oxalic acid. Finally, a model has been proposed for the interaction between the zinc oxalate conversion coating and the corrosion products in which the retention of these products on the surface is promoted by the conversion coating and the surface layer becomes thicker and more compact with time of exposure. These observations explain the increased impedance observed with the test time associated to this coating. The obtained results allowed concluding that the conversion coating of zinc oxalate formed in solution with 10-1 M of oxalic acid results in effective protection of the metallic substrate besides promoting good adhesion with a layer of varnish. These results indicate the potential of this treatment as preparation of zinc surfaces that will be covered with organic coatings (paints, varnishes or lacquers).

Le parasite Varroa destructor provoque depuis plus de 30 ans la perte de nombreuses colonies à travers le monde. L’utilisation d’acaricides de synthèse s’est avérée inefficace au Canada et ailleurs dans le monde à la suite de la sélection de varroas résistants. Dans ce contexte, il est devenu impératif de trouver de nouveaux moyens pour contrôler cette peste apicole. Ce travail original de recherche a pour but de déterminer les paramètres fondamentaux d’une lutte intégrée contre la varroase fondée sur l’utilisation périodique de différents pesticides organiques (l’acide oxalique, l’acide formique et le thymol) associée à des seuils d’interventions. Les seuils d’intervention ont été déterminés à l’aide de régressions linéaires entre les taux de parasitisme par V. destructor et la formance zootechnique des colonies d’abeilles mellifères (production de miel et force des colonies). Un total de 154 colonies d’abeilles du Centre de recherche en sciences animales de Deschambault (CRSAD) ont été suivies de septembre 2005 à septembre 2006. Les seuils calculés et proposés à la suite de cette recherche sont de 2 varroas par jour (chute naturelle) au début mai, 10 varroas par jour à la fin juillet et de 9 varroas par jour au début septembre. L’efficacité des traitements organiques avec l’acide oxalique (AO), l’acide formique (AF) et le thymol a été vérifiée en mai (avant la première miellée) en juillet (entre deux miellées), en septembre (après la miellée et pendant le nourrissage des colonies) et en novembre (avant l’hivernage). L’acide oxalique a été appliqué en utilisant la méthode d’égouttement (4% d’AO p/v dans un sirop de sucrose 1 :1 p/v). L’acide formique a été appliquée sous forme de MiteAwayII™ (tampon commercial imbibé d’AF 65% v/v placé sur le dessus des cadres à couvain), Mitewipe (tampons Dri-Loc™ 10/15cm imbibés de 35 mL d’AF 65% v/v placés sur le dessus des cadres à couvain) ou Flash (AF 65% coulé directement sur le plateau inférieur d’une colonie, 2 mL par cadre avec abeilles). Le thymol a été appliqué sous forme d’Apiguard™ (gélose contenant 25% de thymol p/v placée sur le dessus des cadres à couvain). Les essais d’efficacité ont été réalisés de 2006 à 2008 sur un total de 170 colonies (98 appartenant au CRSAD et 72 appartenant au privé). Les résultats montrent que les traitements de printemps testés ont une faible efficacité pour le contrôle des varroas qui sont en pleine croissance durant cette période. Un traitement avec l’AF à la mi-été permet de réduire les taux de parasites sous le seuil en septembre mais il y a risque de contaminer la récolte de miel avec des résidus d’AF. Les traitements en septembre avec le MiteAwayII™ suivis par un traitement à l’acide oxalique en novembre (5 mL par égouttement entre chaque cadre avec abeilles, 4% d’AO p/v dans un sirop de sucrose 1 :1 p/v) sont les plus efficaces : ils réduisent les niveaux de varroase sous le seuil de 2 varroas par jour au printemps. Nos résultats montrent également que les traitements réalisés tôt en septembre sont plus efficaces et produisent des colonies plus fortes au printemps comparativement à un traitement réalisé un mois plus tard en octobre. En conclusion, ce travail de recherche démontre qu’il est possible de contenir le développement de la varroase dans les ruchers au Québec en utilisant une méthode de lutte intégrée basée sur une combinaison d’applications d’acaricides organiques associée à des seuils d’intervention. / For nearly 30 years, Varroa destructor has been responsible for the loss of many honey bee colonies around the world. The continued use of synthetic acaricides has resulted in their reduced efficacy against this pest in Canada and in other countries because of the selection of resistant mite populations. With this situation still present, it has become of utmost importance to develop efficient methods to control this apicultural pest. The major goal of this original work is to determine the fundamental parameters underlying the use of an integrated pest management (IPM) strategy against the varroa mite. The IPM strategy developed in this research is based on the periodic use of organic pesticides (oxalic acid, formic acid and thymol) and treatment threshold. Treatment thresholds were determined from linear regressions between the varroa mite levels and the zootechnical performances (honey production and colony strength) of honey bee colonies. A total of 154 honey bee colonies from the livestock of the “Centre de recherche en sciences animales de Deschambault” (CRSAD) were monitored from September 2005 to September 2006. Based on our findings, we propose economic treatment thresholds for three periods in the year: early May, late July and early September that are respectively 2, 10 and 9 varroa mites per day. Efficacy of the various organic treatments: formic acid (FA), oxalic acid (OA) and thymol was evaluated in May (before the first honey flow), in July between two honey flows, in September (after the honey flow and before the fall feeding of colonies) and in November (before wintering). OA was applied using the trickling method (4% OA w/v in a sucrose syrup 1:1 w/v). FA was applied using MiteAwayII™ (pads imbedded with FA 65% v/v placed on top of brood frames), Mitewipe (Dri-Loc™ pads 10/15cm imbedded with 35 mL FA 65% v/v placed on top of brood frames), Flash (FA 65% poured directly on the bottom board of colonies, 2 mL per frame with bees). Thymol was applied using Apiguard™ (gel with 25% de thymol w/v placed on top of the brood frames). Efficacy trials were realised from 2006 to 2008 on a total of 170 colonies (98 from the CRSAD and 72 owned by a commercial beekeeper). Results show that treatments applied in spring give low efficacy on reducing varroa mite populations that are in full growth at this time because of large amounts of brood available for mite reproduction. Application of a FA treatment in mid-summer offers the opportunity to reduce mite populations at the 11 mites per day September threshold but FA summer application is accompanied by a risk of incorporating residues in the harvested honey. Application of MiteAwayII™ in September followed by an oxalic acid treatment in November (trickling method 4% OA w/v in a sucrose syrup 1 :1 w/v, 5 mL between frames with bees) gave the best efficacy results: varroa mite levels are reduced below the 2 mites per day spring threshold. Our results also show that an early September management strategy of colonies for winter preparation (varroa treatment and fall feeding) gives greater varroa control, higher colony winter survival and stronger colonies in spring when compared to a later treatment in October. In conclusion, this work shows that varroa mite control in honey bee colonies in Québec is possible by using an integrated pest management strategy based on the application of a combination of organic acaricides in association with treatment thresholds.

This thesis examines and tests acids and conditions, which make the production of nanoporous ceramic at the thin aluminium layer the most effective and provide the highest quality. This paper describes the production of nanoporous structures with pore size 15-400 nm, depending on the electrolyte. Creating a regular hexagonal structure by electrochemical oxidation is dependent on many parameters that affect the regularity of structure and parameters of the ceramics produced. They were investigated primarily by changes in temperature and input voltage. All results were examined by SEM analysis.

No description available.

An effective procedure and parameter window was developed for underwater friction stir welding (UWFSW) 304L stainless steel with a PCBN tool. UWFSW produced statistically significant: increases in yield strengths, decreases in percent elongation. The ultimate tensile strength was found to be significantly higher at certain parameters. Although sigma was identified in the UWFSWs, a significant reduction of sigma was found in UWFSWs compared to ambient FSWs. The degree of sensitization in UWFSWs was evaluated using double loop EPR testing and oxalic acid electro-etched metallography. Results were compared to base metal, ambient FSW, and arc welds. Upper and lower sensitization localization bands were identified in the UWFSWs. Although higher sensitization levels were present in UWFSWs compared to the arc weld, ambient FSW, and heat treated base metals, the UWFSWs were found less susceptible to corrosion than arc welds due to the subsurface location of the sensitization bands. A SCC analysis of UWFSWs relative to base metal and arc weldments was performed. U-bends were exposed to two 3.5% NaCl cyclic immersion experiments at 21 °C and 63 °C for 1000 hours each. A tertiary test was conducted in a 25% NaCl boiling solution. The UWFSW u-bends were no more susceptible to SCC than base metal in the cyclic immersion tests. In the boiling NaCl test, the SCC of the UWFSWs showed significant improvement over the SCC of arc welds. Arc u-bends cracked entirely within the weld bead and HAZ, while SCC in the UWFSWs showed no cracking localization.

The atomic metal anions Rb-, Cs-, Cu-, Ag- and Fe- have been generated in the gas phase and reacted with various neutral reactants in a triple quadrupole mass spectrometer. The metal anions were formed via electrospray ionization of the metal-oxalate solutions and form in gas phase between the capillary and the first quadrupole. Neutral gas phase reactants investigated include NO, NO2, SO2, C6F5OH, C6F5NH2, C6F6, E-octafluoro-butene and 1,2,3/1,2,4/1,3,5 trifluoro-benzene. When possible, CBS-4M methods were used to suggest the lowest energy products based on relative energy. Observed reactions of atomic metal anions with the aforementioned neutral species include electron transfer and dissociative electron transfer to the neutral gas phase reactants. In addition, hydrogen abstraction and fluorine abstraction forming a neutral metal hydride or fluoride as well as the formation of multiply substituted metal-oxide/fluoride anions was also observed. Metal-complex anions observed from the gas phase reactions include CuF-,CuF2-,CuO-,CuO2-, FeO-, FeO2-, FeO3-, FeF-, FeF2-, FeF3-, CsF- and CsF2-.

The atomic metal anions Rb-, Cs-, Cu-, Ag- and Fe- have been generated in the gas phase and reacted with various neutral reactants in a triple quadrupole mass spectrometer. The metal anions were formed via electrospray ionization of the metal-oxalate solutions and form in gas phase between the capillary and the first quadrupole. Neutral gas phase reactants investigated include NO, NO2, SO2, C6F5OH, C6F5NH2, C6F6, E-octafluoro-butene and 1,2,3/1,2,4/1,3,5 trifluoro-benzene. When possible, CBS-4M methods were used to suggest the lowest energy products based on relative energy. Observed reactions of atomic metal anions with the aforementioned neutral species include electron transfer and dissociative electron transfer to the neutral gas phase reactants. In addition, hydrogen abstraction and fluorine abstraction forming a neutral metal hydride or fluoride as well as the formation of multiply substituted metal-oxide/fluoride anions was also observed. Metal-complex anions observed from the gas phase reactions include CuF-,CuF2-,CuO-,CuO2-, FeO-, FeO2-, FeO3-, FeF-, FeF2-, FeF3-, CsF- and CsF2-.