Corrosión inducida por contaminantes hidrosolubles en la intercara metal/pintura

El objetivo principal de este trabajo es profundizar en el conocimiento del fenómeno de la corrosión subpelicular inducida por contaminantes hidrosolubles en la intercara metal/pintura. La contaminación salina del substrato es una situación común en la práctica: la superficie metálica suele estar expuesta a atmósferas contaminadas antes de ser recubierta, limpieza previa del metal con abrasivos contaminados, etc. La eliminación total de estos contaminantes resulta muy difícil de conseguir incluso con las técnicas más sofisticadas de limpieza. Esta investigación se centra en la determinación del efecto de la naturaleza del contaminante y la naturaleza y espesor del recubrimiento en el proceso de corrosión subpelicular del acero. En la investigación se utilizaron dos barnices de naturaleza diferente: poliuretano y vinílico; y se aplicaron a tres espesores diferentes. Los contaminantes empleados en este trabajo fueron: NaCl, NH4C1, CaCl2, Na2S04, (NH4)2S04, NaN03, NH4N03, Ca(N03)2. Los ensayos se realizaron en una cámara de condensación de humedad permanente. Los tiempos de exposición fueron 100, 300 y 600 horas. La velocidad de corrosión se evaluó gravimétricamente, mediante la técnica de pérdida de peso. Se realizaron estudios de permeabilidad al oxígeno y al agua de películas libres de substrato, evaluación de la velocidad de corrosión de probetas sin pintar inmersas en soluciones salinas de los contaminantes seleccionados, conductividad de dichas soluciones salinas, solubilidad del oxígeno en las soluciones salinas, adherencia en seco y en húmedo a diferentes tiempos de exposición. Se aporta evidencia respecto al control ejercido en el proceso corrosivo por el oxígeno que permea a través de la película, mientras que la permeación de agua controla la pérdida de adherencia del recubrimiento. Ambas permeabilidades dependen de la naturaleza del recubrimiento y de su espesor. Se ha investigado la influencia de la naturaleza del contaminante en la intercara metal/pintura. La naturaleza del catión parece quedar enmascarada por el efecto definitivo del anión. La concentración salina ejerce asimismo un efecto importante en la corrosión subpelicular. ABSTRACT The main aim of this work is to study in depth the knowledge of underfilm corrosión induced by hydrosoluble contaminants at the metal/paint Ínterface. The saline contamination of the substrate is a common situation in practice: metallic surfaces use to be exposed to polluted atmospheres, previous cleaning of the metal with contaminated abrasives, etc. Total elimination of these contaminants is hard to obtain even with modern cleaning techniques. This research is focused in determining the effect of contaminant nature, coating nature and its thickness on the steel underfilm corrosión process. In this work we used two varnishes with different nature: polyurethane and vinyl; they were applied in three different thicknesses. The saline contaminants employed were: NaCl, NH4C1, CaCl2, Na2S04, (NH4)2S04, NaN03, NH4N03/ Ca(N03)2. The tests were carried out in a condensation humidity chamber. The period of exposure were 100, 300 and 600 hours. Corrosión rate was assessed by weight loss. Simultaneously, studies on oxygen and water permeability of free films, assessing on corrosión rate of uncoated samples immersed in saline solutions of the selected contaminants, conductivity of these solutions, oxygen solubility in saline solutions, wet and dry adhesión of the polyurethane varnish at different periods of exposure, were carried out. There is clear evidence about control on corrosión process of oxygen that passes through the coating, while the passing of water controls the loss of adhesión of the coating. Both, water and oxygen permeation, depend on the nature and thickness of the coating. It has been researched the inf luence of the nature of contaminant at the metal/paint interface. The nature of the catión seems to be "masked" by the definitive effect of the nature of anión. The saline concentration also exerts an important effect on underfilm corrosión.

Lipophilic antifolates as potential antipsoriatic agents

The lipophilic dihydrofolate reductase (DHFR) inhibitor m-azidopyrimethamine (MZP) was investigated for suitability for development as a topical antipsoriatic agent. The clinical features and treatments for psoriasis were reviewed. High performance liquid chromatography (HPLC) was employed as the main analytical method, with UV spectroscopy being used in some cases. Reduction of the azido-group was proposed as a potential detoxification mechanism for MZP. The rates of reduction of a series of substituted phenyl azide compounds by dithiothreitol were investigated and found to depend on the substitution pattern of the aryl azide molecular, with electron deficient azides exhibiting faster rates of reduction in the system studied. The rates of reduction of MZP and analogous compounds were also studied using this model. The skin penetration of MZP was assessed using an in vitro hairless mouse skin model. The rate of permeation (flux) of MZP across hairless mouse skin was found to be dependent on the quantity of propylene glycol used as cosolvent in the vehicle and the pH. The use of a pretreatment regime of oleic acid in propylene glycol was shown to greatly increase the penetration of MZP through the hairless mouse skin as compared to application without pretreatment, or pretreatment with other penetration enhancers. The metabolism of MZP was studied in in vitro models comprising skin homogenates, SV-K14 human keratinocyte cell cultures and skin commensal bacterial cultures. No conversion of MZP to the corresponding amine was detected in any of the models. The growth inhibitory properties of MZP were investigated in an in vitro SV-K14 human keratinocyte cell culture model and compared with those of other DHFR inhibitors. [14C]-pyrimethamine was shown to be taken up by the SV-K14 keratinocytes.

Desenvolvimento de material BaCexPr1-xO3 (0 ≤ X ≤ 1) com estrutura perovskita para oxidação catalítica do CO a CO2 em reator de leito fixo

Barium Cerate (BaCeO3) is perovskite type structure of ABO3, wherein A and B are metal cations. These materials, or doped, have been studied by having characteristics that make them promising for the application in fuel cells solid oxide, hydrogen and oxygen permeation, as catalysts, etc .. However, as the ceramic materials mixed conductivity have been produced by different synthesis methods, some conditions directly influence the final properties, one of the most important doping Site B, which may have direct influence on the crystallite size, which in turn directly influences their catalytic activity. In this study, perovskite-type (BaCexO3) had cerium gradually replaced by praseodymium to obtain ternary type materials BaCexPr1-xO3 and BaPrO3 binaries. These materials were synthesized by EDTA/Citrate complexing method and the material characterized via XRD, SEM and BET for the identification of their structure, morphology and surface area. Moreover were performed on all materials, catalytic test in a fixed bed reactor for the identification of that person responsible for complete conversion of CO to CO2 at low operating temperature, which step can be used as the subsequent production of synthesis gas (CO + H2) from methane oxidation. In the present work the crystalline phase having the orthorhombic structure was obtained for all compositions, with a morphology consisting of agglomerated particles being more pronounced with increasing praseodymium in the crystal structure. The average crystal size was between 100 nm and 142,2 nm. The surface areas were 2,62 m²g-1 for the BaCeO3 composition, 3,03 m²g-1 to BaCe0,5Pr0,5O3 composition and 2,37 m²g-1 to BaPrO3 composition. Regarding the catalytic tests, we can conclude that the optimal flow reactor operation was 50 ml / min and the composition regarding the maximum rate of conversion to the lowest temperature was BaCeO3 to 400° C. Meanwhile, there was found that the partially replaced by praseodymium, cerium, there was a decrease in the catalytic activity of the material.

Caractérisation de l'impact des conditions opératoires sur l'efficience d'un procédé de concentration du lait par ultrafiltration

Les concentrés de protéines de lait sont couramment utilisés comme ingrédients lors de la standardisation du lait de fromagerie. La concentration des protéines est généralement réalisée par ultrafiltration (UF) à l’aide de membranes polymériques ayant un seuil de coupure de 10 kDa, et ce, jusqu’à un facteur de concentration volumique de 3.5X. Dans l’optique d’améliorer l’efficience du procédé d’UF, l’étude avait pour but de caractériser l’impact du mode opératoire (pression transmembranaire constante (465 et 672 kPa) et flux constant) ainsi que la température (10°C et 50°C) sur la performance du système jusqu’à un facteur de concentration volumique de 3.6X. Le module de filtration à l’échelle pilote comprenait une membrane d’UF en polyéthersulfone de 10 kDa d’une surface de 2,04 m2. La performance du système a été caractérisée sur le flux de perméation, la sélectivité et la consommation énergétique totale. L’étude a montré que le flux de perméation était 1,9 fois plus élevé à une température de 50°C comparativement à 10°C lors de l’UF du lait. Le coefficient de rejet des protéines n’a pas été affecté significativement par la pression transmembranaire et la température (P< 0,05). L’effet de la température a été observé au niveau de la teneur en calcium, laquelle était plus élevée de 12% dans les rétentats générés à 50C. La consommation énergétique totale du système d’UF était plus élevée à 10C comparativement à 50C, représentant 0,32±0,02 et 0,26±0,04 kWh/kg rétentat respectivement. Les résultats montrent que le ratio d’efficience énergétique (rapport entre le flux de perméation et la consommation énergétique) optimal a été obtenu à faible pression transmembranaire constante et à 50C. L’approche développée dans le cadre de ce projet fournira des outils aux industriels laitiers pour améliorer l’éco-efficience de leurs procédés de séparation baromembranaire.

Influence of autogenous shrinkage on mass transport properties of concrete

La retracción autógena en el hormigón es el cambio volumétrico una vez iniciado su proceso de fraguado. Se desarrolla a edades muy tempranas debido a la retracción química y a la autodesecación. Éstos causan microfisuras en hormigones de alta resistencia y permiten el ingreso de agentes nocivos como dióxido de carbono, cloruros y sulfatos que deterioran al hormigón. A pesar de haber estudios de la retracción autógena, existe incertidumbre sobre su influencia en la durabilidad del hormigón. Por ello, el motivo del presente estudio es cuantificar y analizar el efecto de la retracción autógena en el hormigón usando tres pruebas de transporte: difusión de oxígeno, permeabilidad de oxígeno y absorción de agua. Dos métodos, para tres diferentes aglutinantes, fueron usados para determinar la mezcla control que produce menor retracción: utilizando SRA y realizando el curado en un cuarto de niebla. Posteriormente, los resultados de las pruebas de transporte entre la mezcla de control seleccionada y mezclas altamente afectadas por retracción autógena fueron comparados para diferentes aglutinantes. Resultados revelaron que muestras con SRA presentan menores retracciones autógenas y se sugiere que estas muestras sean consideradas de control. Se demostró que la retracción autógena afecta significativamente los coeficientes de transporte los cuales en un punto de vista de servicio pueden reducir la vida útil de cualquier estructura realizada con hormigón de alta resistencia. Esta investigación además confirmó que la mayor deformación autógena ocurre durante las dos primeras semanas; por lo tanto, se debe tomar cuidado suficiente en el curado.

Reduction of oxygen impurity at GaN/beta-Si(3)N(4)/Si interface via SiO(2) to Ga(2)O conversion by exposing of Si surface under Ga flux

The removal of native oxide from Si (1 1 1) surfaces was investigated by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectra (SIMS) depth profiles. Two different oxide removal methods, performed under ultrahigh-vacuum (UHV) conditions, were carried out and compared. The first cleaning method is thermal desorption of oxide at 900 degrees C. The second method is the deposition of metallic gallium followed by redesorption. A significant decrease in oxygen was achieved by thermal desorption at 900 degrees C under UHV conditions. By applying a subsequent Ga deposition/redesorption, a further reduction in oxygen could be achieved. We examine the merits of an alternative oxide desorption method via conversion of the stable SiO(2) surface oxide into a volatile Ca(2)O oxide by a supply of Ga metals. Furthermore, ultra thin films of pure silicon nitride buffer layer were grown on a Si (1 1 1) surface by exposing the surface to radio-frequency (RF) nitrogen plasma followed by GaN growth. The SIMS depth profile shows that the oxygen impurity can be reduced at GaN/beta-Si(3)N(4)/Si interfaces by applying a subsequent Ga deposition/redesorption. (C) 2011 Elsevier B.V. All rights reserved.

Oxygen flux through salmonid spawning gravels

Laboratory and field studies have shown that the survival of salmonid fish eggs and alevins is dependent upon the supply rate or flux of dissolved oxygen through gravel beds used for spawning. Although there have been a number of studies concerned with North American species there are few data for Atlantic salmon (Salmo salar) and the brown trout (S. trutta). For this study intragravel seepage velocities and dissolved oxygen concentrations have been measured throughout the incubation period in spawning gravels utilized by brown trout (Salmo trutta). Variation in the hatching success of batches of trout and salmon (Salmo salar) can, in part, be attributed to a critical threshold of oxygen flux through the gravels.

Dissolved oxygen and O-2 flux across the water-air interface of the Changjiang Estuary in May 2003

The field observation of this study was carried out in the Changjiang Estuary from May 19 to 26,2003, just a few days before the Three Gorges Dam began to store water. A total of 29 stations, including 2 anchor stations, were distributed through almost the whole salinity gradient Based on the data gained from these stations, the biogeochemical characteristics of dissolved oxygen (DO) were examined. Spatial distribution of DO concentrations showed the pattern that it increased in a downriver direction. DO concentration generally varied within a narrow range of 733-8.10 mg l(-1) in the freshwater region and the west part of the mixed water region, and after that it increased rapidly. In vertical direction, the differences in DO concentrations between surface and 2 m above the bottom were big at the stations with water depths exceeding 20 m; DO concentration up to 14.88 mg l(-1) was recorded at the sea surface, while at 2 m above the bottom its concentration was only about 4 mg l(-1). The fluctuation in DO concentrations was small during a period of 48 h in the mixed water region and 2 m above the bottom of the seawater region; while it was large during the same period in the seawater region for surface and 5 m below the surface layer, and a maximum variation from 8.77 to 12.66 mg l(-1) in 4 h was recorded. Oxygen fluxes also showed a marked spatio-temporal variation. As a whole, the freshwater region and mixed water region were an oxygen sink while the seawater region was a source. Relationships between dissolved oxygen and some biogeochemical parameters which could markedly influence its spatio-temporal distribution were discussed in this paper. (C) 2008 Elsevier B.V. All rights reserved.