Medium Mn TRIP steels are amongst the most widely researched third generation advanced high strength steels (3G-AHSSs) as they are ideal candidates for automotive light-weighting applications owing to their superior strength and ductility balance. However, the thermal processing cycles of these steels need to be compatible with the industrial continuous galvanizing line (CGL) in order to successfully employ them in the automotive manufacturing industry. The main objective of the present research was to develop a CGL compatible thermal processing cycle for a prototype medium Mn steel that would produce significant volume fractions of chemically stable retained austenite and exhibit mechanical properties consistent with established 3G-AHSS targets. In that regard, the effects of intercritical annealing (IA) time and temperature and starting microstructure were determined in the first part of this research. The as-received tempered martensite (S-TM) and heat treated martensite (S-M) were the two different starting microstructures studied in this research. In this case, the overaging temperature (OT) treatment (460°C for 20s) was kept constant. It was found that high volume fractions (≥ 0.30) of retained austenite were achieved for S-M samples intercritically annealed at 675°C for shorter times (i.e. 60 to 120s) compared to S-TM samples. TEM analysis of the S-M samples showed that most of the retained austenite was present in a film type morphology, which is known to be more stable chemically and mechanically compared to the block type morphology. The tensile test results showed that although both the S-TM and S-M samples exhibited a high strength/ductility balance, the S-M samples, particularly the S-M 675°C + 120s samples, showed more potential in terms of CGL compatibility and achieving 3G-AHSS target mechanical properties. The effect of OT holding time was determined in the second part of this research. In that regard, the OT holding time was varied form 20s to 120s for selected S-TM and S-M samples. The S-TM 710°C samples with increased OT holding times (60s and 120s) had a significant increase in retained austenite volume fraction compared to the baseline 20s OT samples. However, the retained austenite volume fractions did not change for S-M samples regardless of OT holding time. It was also found that the mechanical properties of the annealed S-TM and S-M steels depended on the OT holding time. For the S-TM samples with > 120s IA holding times, longer OT holding times (60s and 120s) produced chemically unstable retained austenite which transformed rapidly at low strain resulting in low UTS × TE products. However, although longer OT holding times significantly increased the yield strength of the annealed S-M samples, the UTS × TE product decreased significantly owing to decreased retained austenite stability. Finally, based on the results of this research, it was concluded that the prototype medium Mn TRIP steel can achieve 3G-AHSS target mechanical properties using CGL-compatible thermal processing cycles. Moreover, depending on successful reactive wetting, it may be possible to perform both thermal processing and galvanizing of this steel in the industrial CGL. / Thesis / Master of Applied Science (MASc)

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Ce travail s'inscrit dans la recherche et le développement de nouvelles molécules à visée thérapeutique via la mise au point de cyclisations radicalaires oxydatives médiées par l'acétate de manganèse(III). Deux problématiques ont dirigé nos recherches. Tout d'abord, nous avons développé une stratégie de synthèse de prodrogues analogues de la pafuramidine, molécule antileishmanienne. Ainsi, une 1ère série d'amidoximes a été obtenue à partir de β-cétosulfones par une synthèse multi-étapes faisant appel aux réactions i) de cyclisations radicalaires oxydatives médiées par Mn(OAc)3 et ii) de couplages pallado-catalysées de Buchwald-Hartwig et de Heck. Suite à l'évaluation biologique in vitro sur Leishmania donovani et sur des cellules humaines, une 2ème série d'amidoximes et en particulier des monoamidoximes a été réalisée, ce qui a révélé une molécule présentant un index de sélectivité 40 fois plus élevé que celui de la pentamidine, médicament utilisé comme référence. Nous avons également mis au point un double couplage "one-pot" de Buchwald-Hartwig dans le but d'obtenir des produits dicouplés dissymétriques, précurseurs éventuels de futures diamidoximes. Dans une deuxième partie, nous nous sommes focalisés sur la synthèse de composés spirocycliques pouvant constituer un pharmacophore original. De ce fait, une stratégie de synthèse conduisant à divers noyaux tels des tétralines spirocycliques, des spirolactones, des spirobenzophénanthrédin-6(5H)-ones a été mise au point. Ce travail nous a également menés vers la synthèse de dérivés thiobarbiturates, analogues de composés anesthésiques ou anticonvulsivants. / This work focuses on the research and development of new therapeutic molecules through optimized radical cyclizations mediated by manganese(III) acetate. Two problematics directed our research. First, we developed analogous prodrugs of pafuramidine, an antileishmanial molecule. Thus, a 1rst series of amidoximes was obtained from β-ketosulfones by a multi-step synthesis involving i) radical oxidative cyclizations mediated by Mn(OAc)3 and ii) pallado-catalyzed Buchwald-Hartwig and Heck coupling reactions. The 1rst series being biologically evaluated in vitro, both on Leishmania donovani and human cells, a 2nd series and particularly monoamidoximes was prepared and revealed a molecule presenting a selectivity index 40 times higher than the one of pentamidine, used as reference drug compound. We also developed a one-pot double Buchwald-Hartwig coupling reaction in the aim to obtain dissymmetric dicoupled products, potential precursors of future diamidoximes. In a second time, we focused on the synthesis of spirocyclic compounds which could constitute an original pharmacophore. Therefore, we performed a synthesis allowing access to a wide variety of scaffolds such as spirocyclic tetralins, spirolactones, spirobenzophenanthridin-6(5H)-ones. This work allowed the synthesis of thiobarbiturates, analogous of anesthetic or anticonvulsive compounds.

Mobile computing is becoming increasingly important, due to the rise in the number of portable computers and the desire to have continuous network connectivity to the Internet, irrespective of the physical location of the node. We have also seen a steady growth of the market for wireless communication devices. Such devices can only have the effect of increasing the options for making connections to the global Internet. The Internet infrastructure is built on top of a collection of protocols called the TCP/IP protocol suite. Transmission Control Protocol (TCP) and Internet Protocol (IP) are the core protocols in this suite. There are currently two standards: one to support the current IPv4 and one for the upcoming IPv6 [1]. IP requires the location of any node connected to the Internet to be uniquely identified by an assigned IP address. This raises one of the most important issues in mobility because, when a node moves to another physical location, it has to change its IP address. However, the higher-level protocols require the IP address of a node to be fixed for identifying connections. The Mobile Internet Protocol (Mobile IP) is an extension to the Internet Protocol proposed by the Internet Engineering Task Force (IETF) that addresses this issue. It enables mobile devices to stay connected to the Internet regardless of their locations, without changing their IP addresses and, therefore, an ongoing IP session will not be interrupted [2, 3, 4]. More precisely, Mobile IP is a standard protocol that builds on the Internet Protocol by making mobility transparent to applications and higher-level protocols like TCP. However, before Mobile IP can be broadly deployed, there are still several technical barriers, such as long handover periods and packet loss that have to be overcome, in addition to other technical obstacles, including handover performance, security issues and routing efficiency [7]. This study presents an investigation into developing new handover mechanisms based on link layer information in Mobile IP and fast handover in Mobile IPv6 environments. The main goal of the developed mechanisms is to improve the overall IP mobility performance by reducing packet loss, minimizing signalling overheads and reducing the handover processing time. These models include the development of a cross-layer handover scheme using link layer information and Mobile Node (MN) location information to improve the performance of the communication system by reducing transmission delay, packet loss and registration signalling overheads. Finally, the new schemes are developed, tested and validated through a set of experiments to demonstrate the relative merits and capabilities of these schemes.

Sur le site minier de Milluni (Bolivie, Altiplano, 4800 m asl), la contamination des eaux de surface et des sédiments par les métaux lourds a été étudiée en combinant des approches géochimiques, minéralogiques et hydrochimiques. Pour les différents métaux, les sources minérales de la contamination ont été établies, ainsi que les processus géochimiques d'altération des minéraux primaires en minéraux tertiaires. La compréhension des mécanismes géochimiques en jeu et les bilans réalisés ont permis de déterminer les origines et les modes de transport et de contrôle des métaux dans cet environnement. Enfin, les carottages des sédiments lacustres et des tourbières ont permis d'évaluer l'évolution historique de la contamination en métaux lourds, notamment au cours du siècle dernier.

Sem resumo / Sem abstract

Made available in DSpace on 2017-07-24T19:38:12Z (GMT). No. of bitstreams: 1 Gustavo Marciniuk.pdf: 9151594 bytes, checksum: 94a7264c77b0567f7224ef931267fdab (MD5) Previous issue date: 2014-03-11 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work refers to the development of a simple and innovative method for the synthesis of ternary composites of different proportions based on amorphous carbon, polyaniline and manganese (IV) oxide for their future use in electrochemical supercapacitors. The process presented here consists, essentially, of 3 parts: (i) at first, it has been performed the oxidative treatment of amorphous carbon and the separated synthesis of pure MnO2 and polyaniline, when all the materials involved were structurally characterized by XRD, FTIR, RAMAN, DLS and SEM, and electrochemically characterized by cyclic voltammetry measurements, in order to identify its structural, morphological and electrochemical properties and then compared with those presented by the future ternary composites; (ii) synthesis of a binary C/MnO2 composite by the anchoring of the MnO2 particles on the oxidized sites of the amorphous carbon, which represents the first stage on the formation of the ternary composites. Its purpose was to identify possible structural and electrochemical changes caused by MnO2 surface layer in the comparison of the binary composite with its individual components. Therefore, this composite was characterized by the same methods mentioned above; (iii) synthesis and characterization of ternary composites on different proportions, based on the initial formation of binary C/MnO2 followed by in situ polymerization of aniline monomers on their surface structure. The purpose of the synthesis in different proportions is to obtain a response profile when small changes in the quantity of the constituent materials are introduced in the ternary composites. The characterization of the ternary composites were carried out by XRD, FTIR, RAMAN, DLS and SEM, which allow to identify possible structural and morphological changes showed by composites compared to the individual components and, by cyclic voltammetry measurements, when it was possible to notice the electrochemical behavior of these composites and define their specific capacitance values in parallel to their processes of charge storage and ions diffusion. / Neste trabalho, buscou-se desenvolver uma metodologia simples e inovadora para a síntese de compósitos ternários de diversas proporções baseados em carbono amorfo, polianilina e óxido de manganês (IV) visando sua futura utilização em supercapacitores eletroquímicos. O trabalho consiste basicamente de 3 partes; (i) inicialmente realizou-se o tratamento oxidativo do carbono amorfo e a síntese individual dos compostos MnO2 e PAni, onde todos os materiais foram caracterizados estruturalmente por DRX, FTIR, RAMAN, DLS e MEV e eletroquimicamente por medidas de voltametria cíclica, afim identificar suas propriedades estruturais, morfológicas e eletroquímicas e compará-las com as apresentadas pelos futuros compósitos ternários; (ii) síntese de um compósito binário C/MnO2 pelo ancoramento das partículas de MnO2 sobre sítios oxidados do carbono amorfo, a qual configura a 1ª etapa da formação dos compósitos ternários. Sua finalidade foi de identificar as possíveis mudanças estruturais e eletroquímicas ocasionadas pela presença da camada superficial de MnO2 quando comparado o compósito binário aos seus componentes individuais. Para tanto, este compósito foi caracterizado pelos mesmos métodos apresentados acima; (iii) síntese e caracterização de compósitos ternários de diferentes proporções baseados na inicial formação do binário C/MnO2 seguido da polimerização in situ dos monômeros de anilina sobre sua estrutura superficial. A abordagem da síntese em diferentes proporções torna possível a obtenção de um perfil de resposta quando são introduzidas nos compósitos ternários pequenas modificações na quantidade dos materiais constituintes. A caracterização dos compósitos ternários foi realizada pelas técnicas de DRX, FTIR, RAMAN, DLS e MEV, as quais permitem identificar possíveis mudanças estruturais e morfológicas apresentadas pelos compósitos frente aos componentes individuais, e, por medidas de voltametria cíclica, onde foi possível observar o comportamento eletroquímico destes compósitos e definir seus valores de capacitância específica juntamente com seus processos de armazenamento de carga e difusão de íons.

<p>The transport of elements by streams from headwater regions to the sea is influenced by landscape characteristics. This thesis focuses on the influence of landscape characteristics (e.g. proportion of wetland/forest coverage) on temporal and spatial variations of Fe, Mn, S and trace elements (As, Co, Pb) in streams located in northern Sweden, a boreal region characterized by coniferous forests and peat wetlands.</p><p>Water samples from a network of 15 streams revealed a different hydrogeochemistry in forested catchments compared to wetland catchments. The temporal variation was dominated by spring flood, when concentrations of Fe, Mn and trace elements increased in forested headwaters. However, in streams of wetland catchments concentrations decreased, but Pb concentrations were higher in comparison to other streams. Both Fe and Pb showed positive correlations with wetland area, while Co correlated with forest coverage. The anthropogenic contribution of As and Pb appear to be larger than the supply from natural sources.</p><p>During spring flood SO₄^2- decreased in most streams, although concentrations increased in streams of wetland catchments. Concentrations of SO₄^2-were higher in streams of forested catchments than in wetland dominated streams, the former being net exporters of S and the latter net accumulators. Isotope values of stream water SO₄^2- (δ³⁴S_SO4) were close to that of precipitation during spring flood, indicating that the major source of S is from deposition. The results show that, although emissions of anthropogenic S have been reduced, there is still a strong influence of past and current S deposition on runoff in this region.</p><p>In conclusion, wetlands are key areas for the hydrogeochemistry in this boreal landscape. The findings emphasize the importance of understanding stream water chemistry and element cycling from a landscape perspective. This may be important for predicting how boreal regions respond to environmental disturbances such as climate change.</p>

QC 20100927

Metal oxide-facilitated transformation is likely an important degradation pathway of antibacterial agents at soil-water interfaces. Phenolic disinfectants (triclosan and chlorophene), fluoroquinolones (FQs), and aromatic N-oxides are of particular concern due to their widespread usage, potential toxicity and frequent detection in the environment. Results of the present study show that the above antibacterial agents are highly susceptible to metal oxide-facilitated oxidation. The interfacial reactions exhibit complex reaction kinetics, which are affected by solution pH, the presence of co-solutes, surface properties of metal oxides, and structural characteristics of antibacterial agents. Adsorption of the antibacterial agents to Mn and Fe oxide surfaces generally proceeds faster than oxidation reactions of these compounds by Mn and Fe oxides, especially in the case of Fe oxides. Reaction intermediates and end products are identified by GC/MS, LC/MS and/or FTIR. Structurally-related model compounds are examined to facilitate reaction site and mechanism elucidation. On the basis of experimental results and literature, reaction schemes are proposed. In general, the antibacterial agent is adsorbed to the oxide surface, forming a precursor complex. Electrons are transferred within the precursor complex from the antibacterial agent to the oxide, followed by releasing of the radical intermediates which undergo further reactions to generate oxidation products. The precursor complex formation and electron transfer are likely rate-limiting. For triclosan, phenoxy radicals are critical intermediates to form oxidation products through three pathways (i.e., radical coupling, further oxidation of the radical, and breakdown of an ether bond within the radical). The first two pathways are also operative in the oxidation of chlorophene. For FQs, oxidation generates radical intermediates that are most likely centered on the inner N in the piperazine ring. The radical intermediates then undergo three major pathways (i.e., radical coupling, N-dealkylation, and hydroxylation) to yield a variety of products. For aromatic N-oxides, a N-oxide radical intermediate is generated upon oxidation by MnO2, followed by the loss of oxygen from the N-oxide moiety and the formation of a hydroxyl group at the C-atom adjacent to the N-oxide moiety. Overall, a fundamental understanding of the reaction mechanisms between three classes of antibacterial agents and metal oxides has been obtained.