Schwermetallsalze wie beispielsweise Aluminium- oder Eisensalze werden in der Abwasserbehandlung zur Prävention und Bekämpfung von Blähschlamm, Schwimmschlamm und Schaumbildung verwendet. Dadurch kann eine Verbesserung der Schlammabsetzeigenschaften im Nachklärbecken erreicht werden. Übermäßiges Wachstum des grampositiven Bakteriums Microthrix parvicella gilt dabei als Hauptursache von Schlammabsetzproblemen und kann ebenfalls durch die Dosierung von schwermetallhaltigen Flockungs- und Fällungsmitteln vermieden werden. Da diese Verbindungen in Wasser gelöst sind, müssen sie die Außenmembran bestimmter Bakterien passieren. Nur der Einbau von wassergefüllten Kanälen erlaubt den gelösten Salzen das Passieren der durch hydrophobe Fettsäuren aufgebauten zusätzlichen Permeabilitätsbarriere. In dieser Arbeit wurden wassergefüllten Kanäle von Microthrix parvicella isoliert, aufgereinigt und mit Hilfe der Black-Lipid-Bilayer-Technik charakterisiert. Ergänzend wurde der Einfluss und der Durchlass der Flockungs- und Fällungsmittel in Titrationsexperimenten untersucht. Dabei konnte ein wassergefüllter Kanal, der die Bezeichnung MppA erhielt, gefunden werden, welcher eine Leitfähigkeit von 600 pS in 1 M Kaliumchlorid und eine Bindestelle für mehrwertige Kationen wie Eisen oder Aluminium zeigte. Die Bindung dieser mehrwertigen Kationen führte zu einer Änderung der Ionenselektivität. Ohne Bindung mehrwertiger Kationen zeigte der Kanal eine leichte Kationenselektivität. Nach der Bindung wechselte die Ionenselektivität zu einer Anionenselektivität, was auf eine spezifische Ladungsverteilung im Kanal hinweist. Der Kanal MppA zeigte gleichwertige Bindekonstanten für Aluminium und Eisen. Beide Metalle werden als Fällungs- und Flockungsmittel in Kläranlagen zum Verhindern von Schwimm- und Blähschlamm verwendet. Frühere Arbeiten offenbarten bereits, dass hauptsächlich der Aluminiumanteil entscheidend für die Wirkung dieser Mittel ist. Diese Beobachtungen in Verbindung mit den Ergebnissen dieser Arbeit führten zu der Annahme, dass Eisen und Aluminium eine kompetitive Bindung an der Bindestelle im Kanalinneren zeigen könnten. So könnte in manchen Fällen Aluminium anstelle des sonst als Spurenelement benötigten Eisens durch den Kanal transportiert werden und in Enzym-Substrat-Komplexen eingebaut werden. Dadurch könnten toxische Effekte auftreten, die letztlich ein Absterben des Organismus zur Folge hätten. Für die Bindung der Metallsalze konnte zusätzlich eine pH-Abhängigkeit beobachtet werden. Nur eine Zugabe von Metalllösungen mit einem pH-Wert kleiner 6 führte zu einer Bindung im Kanal. Die Zugabe von Metalllösungen mit einem pH-Wert größer 6 zeigte keinen Effekt auf die Leitfähigkeit des Kanals. Diese Ergebnisse bestätigen die auf Kläranlagen und in vorherigen Arbeiten getätigte Beobachtung, dass der pH-Wert für die Wirksamkeit der Verbindungen entscheidend ist. In dieser Arbeit konnte jedoch erstmals gezeigt werden, dass der pH-Wert direkt die Bindung der Metallsalze beeinflusst. / Heavy metal salts like aluminium or iron compounds are used in waste water treatment plants to prevent bulking sludge, floating sludge and foaming and for this reason to enhance the settleability of the sludge flocs in the secondary clarifier. Excessive growth of the Gram-positive bacterium Microthrix parvicella is one of the main origins of sludge settlement problems and can be avoided by the dosage of heavy metal salts containing flocculation and precipitations agents as well. As these agents are dissolved in water, they have to pass the outer membrane of certain bacteria. Only the incorporation of water-filled channels into the membrane allows the solutes to pass this second permeability barrier build out of hydrophobic fatty acids. In this study, the water-filled channels of Microthrix parvicella were characterized with black lipid bilayer assays and the influence and the pass through of the flocculation and precipitations agents were investigated in titration experiments. A water-filled channel called MppA with a conductance of 600 pS in 1 M potassium chloride could be found which has a binding site for polyvalent cations like iron or aluminium. The binding of polyvalent cations to the binding site inside the channel led to a switch in the ion selectivity. Without binding of polyvalent cations, the channel showed slight cation selectivity. After the binding the selectivity switched to an anion selectivity indicating a special charge distribution in the channel. The channel MppA which was found in Microthrix parvicella showed same binding constants for aluminium and iron. Both metals are used as precipitation and flocculation agents and to prevent bulking sludge and floating sludge in waste water treatment plants. Other former works revealed already that only the aluminium part is decisive for the effect of these agents. These observations in addition to the results of this work led to the suggestion that iron and aluminium show a competitive binding to the binding site. In some cases aluminium might be transported through the channel and incorporated to some enzyme-substrate-complexes instead of the iron which usually acts as a micronutrient. This could lead to toxic effects and the dieback of the organism. A pH-dependency could be found for the binding of the metal salts. Only the addition of metal solutions with a pH lower than 6 led to a binding. The addition of solutions with pH-values higher than 6 showed no effect to the conductivity of the channel. These results confirm the observation done on waste water treatment plants and in other former studies that the pH value is generally decisive for the effect of the agents. But this work could show for the first time that the pH directly affects the binding of the metal salts.

The corrosion protection of aluminium alloys is of high importance, particularly in the aerospace industry. The most widely used technologies utilise Chromium(VI) compounds for conversion coatings and primer additives in paint systems to provide corrosion protection to these alloys. These compounds are highly toxic, carcinogenic and detrimental to the environment, therefore the identification of alternative systems that are safe and environmentally benign, that meet or exceed the current levels of corrosion protection is vital. This research program examines the corrosion inhibition effectiveness of selected rare earth diphenyl phosphates (RE(dpp)3). These compounds incorporate known inhibitor species, namely rare earth metals, organics and phosphates into a single complex, with the aim of achieving synergistic inhibition in corrosive environments. A screening study utilising immersion and weight loss experiments identified Cerium diphenyl phosphate (Ce(dpp)3) and Mischmetal diphenyl phosphate (Mm(dpp)3) as the most effective inhibitors of corrosion for AA2024-T3. The inhibiting efficiency, mechanism of inhibition and surface interaction of these complexes on aluminium alloy AA2024-T3 was characterised using a range of electrochemical and surface techniques. A similar study was carried out using AA7075-T6 to assess the adaptability of the RE(dpp)3 compounds to protect different alloy compositions. The complexes were effective in significantly reducing the corrosion rate of the alloys, with both the cathodic and anodic corrosion processes being suppressed. This mixed inhibition was not attained with the constituent rare earth and diphenyl phosphate ions individually, indicating the need for the complex to remain intact in solution to achieve the high level of corrosion protection observed. The initiation and propagation of surface pits was effectively suppressed by the RE(dpp)3 complexes. The combination of electrochemical and surface characterisation techniques has for the first time allowed insights into the mechanism of action of these compounds on aluminium alloys, and indicated deposition was initiated at electrochemically active intermetallic particles. The mixed rare earth phases present in Mm(dpp)3 produced a synergistic effect, providing a greater degree of corrosion protection compared with Ce(dpp)3, particularly on AA2024-T3. In the final phase of this research project the RE(dpp)3 inhibitor compounds were incorporated into an epoxy coating system, and demonstrated that the initiation of filiform corrosion on AA2024-T3 could be reduced by up to a factor of 3 by their addition. The growth rate of filaments was also impeded.

Increasing concern over the environmental impact of motor vehicles is driving the need for the development of lighter materials to reduce automobile weight and fuel consumption. Sintered aluminium alloys, with their high strength to weight ratios, have potential applications in the automotive industry, but conventional pressed-and-sintered materials have poor mechanical properties due to the presence of residual porosity in the sintered compact. Residual porosity can be eliminated by Hot Isostatic Pressing (HIPing) or combined sinter-HIPing, but these processes are expensive due to the high gas pressures involved, up to several hundred MPa, and also pose a significant safety hazard. There is a limited amount of evidence in the literature suggesting that applied gas pressures as low as a few MPa may be beneficial to the sintering of aluminium alloys, and it is this idea that the present work explores. Compacts of aluminium alloy 2712 (Al-3.8Cu-1Mg-0.7Si-0.1Sn) were prepared from elemental powders and sintered at 590ºC for up to 60 minutes in a horizontal tube furnace under constant flowing nitrogen or argon at pressures up to 600 kPa. Archimedes’ method was used to measure the density of sintered compacts, and the amount of open and closed porosity. Increasing the nitrogen pressure at the start of the isothermal holding stage to 160 kPa increased the sintering rate compared to standard atmospheric pressure sintering. Increasing the nitrogen pressure further, up to 600 kPa, had no additional benefit. The sintering rate was increased further by applying a 600 kPa nitrogen pressure during both heating and isothermal holding. The elevated nitrogen pressure had a negligible effect on the maximum sintered density achieved, and sintering in argon at elevated pressures had no measurable effect on the sintered density or sintering rate. It was shown that the elevated pressure aids in the closure of pores open to the specimen surface, contrary to HIPing and sinter-HIPing, where the pores must be isolated prior to the application of pressure. It was also shown that at 600 kPa nitrogen pressure, the sintered density was independent of the presence of tin in the alloy. The improvements to sintering seem to be related to the formation of aluminium nitride.

Multilayered aluminium alloy composites were produced by accumulative roll bonding (ARB) to very high strain to generate sheet materials consisting of either 32 or 64 alternating layers of Al and Al-0.3w.%Sc alloy. Based on the starting heat treatment condition of the Al(Sc) alloy and the roll bonding temperature, several different Al/Al(Sc) combinations were produced: (i) SSSS-ARB (Al(Sc) in the supersaturated condition; Tdef = 200 ???C; 32 layers); (ii) Aged-ARB (Al(Sc) in the artificially aged condition; Tdef = 200 ???C; 32 layers), and (iii) SSSS-ARB-HT (Al(Sc) in the SSSS condition; Tdef = 350 ???C; 64 layers). Regardless of the roll bonding conditions, Al(Sc) in the form of a dispersion of ultrafine Al3Sc particles strongly impedes structural changes during thermomechanical processing whereas Al readily undergoes extensive dynamic and static restoration. The major aim of the thesis is to understand the effect of initial microstructure and processing conditions on microstructural development in these multilayered Al/Al(Sc) composites. The microstructures were investigated mainly by backscatter electron (BSE) and ion channeling contrast (ICC) imaging in the DualBeam Platform and transmission electron microscopy (TEM) whereas the crystallographic nature of the microstructures were investigated by electron backscatter diffraction (EBSD) and the various diffraction techniques available in the TEM. The mechanical properties of the materials were investigated by hardness and tensile testing. The deformation microstructure and texture of these two alloy combinations were strongly influenced by both the initial heat treatment condition of the Al(Sc) alloy whereby large-scale shear bands are generated during rolling when a dispersion of fine Al3Sc particles is present in the Al(Sc) layers. The deformation mechanism of both SSSS-ARB and Aged-ARB was strongly controlled by the relative hardening behaviour of adjacent layers. In Aged-ARB, a higher magnitude of in-plane shear stress, exceeding the flow stress of Al(Sc), was operative at the interfaces between layers; this was shown to cause the shear banding in this material. All materials were annealed for up to 6h at 350 ??C. This extended annealing generated alternating layers of coarse grains (Al layers) and a recovered substructure (Al(Sc) layers) with the substantial waviness of the layers in both Aged-ARB and SSSS-ARB-HT being inherited from the as-deformed material. While the Al(Sc) layers remain unrecrystallized in all materials due to particle pinning effects, the Al layers underwent continuous and discontinuous recrystallization after low and high temperature roll bonding, respectively. Shear banding in Aged-ARB also resulted in a reduction in intensity of the rolling texture components and had a randomizing effect on the recrystallization texture of the Al layers. The Al/A(Sc) multilayered composites were found to conform to the classic inverse strength/ductility relationship and no significant improvement in ductility (for a given strength) was evident. The barriers to achieving an excellent combination of ductility and strength (i.e. toughness) in these materials were identified to be delamination of the layers, which can be largely reduced (or eliminated) by careful control of starting materials (heat treatment condition and thickness) as well as the processing parameters during ARB.

No description available.

Arbetet redovisar ett projektarbete som utförts på AB Lundbergs Pressgjuteri i Vrigstad där planhetsavvikelser av en specifik detalj har analyserats. Analyserna har tagit hänsyn till både yttre och inre faktorer i gjuteriprocessen och resultat visar att kylningen av detaljen har en betydande inverkan på detaljens planhet.

La tesis se ha centrado en el estudio las diferentes respuestas a la toxicidad por aluminio en tres especies del genero Brachiaria (gramíneas forrajeras de importancia económica) con el fin de contribuir a una mejor comprensión de los mecanismos de resistencia del Al. La investigación se dividió en 5 capítulos. En el primer capítulo se evaluó la respuesta de tres especies del genero Brachiaria a la toxicidad del aluminio. Brachiaria decumbens, B. brizantha y B. ruziziensis fueron crecidas en solución nutritiva completa de baja fuerza iónica y pH ácidos. Se realizaron ensayos para las respuestas al aluminio tales como el crecimiento radicular, primer síntoma de toxicidad y la capacidad para mantener la homeostasis adecuada de nutrientes. En el segundo capítulo hemos utilizado diferentes métodos de tinción para analizar los efectos tóxicos y la distribución de aluminio en el ápice de las especies de Brachiaria. Para la observación del efecto del aluminio y ubicación del aluminio en los ápices de las raíces se utilizaron varias técnicas de tinción: tinción con lumogallion-DAPI, morin y su posterior observación al microscopio confocal. B. decumbens es más eficiente en la exclusión del aluminio, en esta especie fue observada la formación de pelos radiculares, los cuales se desarrollan muy cerca del ápice, contribuyendo a una baja acumulación de aluminio en zonas sensibles. En el tercer capítulo fueron observadas las superficies radiculares para dos especies de Brachiaria, B. decumbens y B. brizantha, utilizando los microscopios SEM-EDX y TEM. Esto con el fin de estudiar los posibles cambios en la estructura y ultraestructura de las plantas en respuesta al aluminio. El Al indujo alteraciones estructurales y ultraestructurales en ambas especies de Brachiaria. Sin embargo, la especie más tolerante al aluminio, B. decumbens, mostró una recuperación después de 96h de exposición a Al. Estos resultados indican el carácter inducible de la tolerancia mecanismo de Al en B. decumbens. En el cuarto capítulo se realizo un análisis de sustancias fenólicas con el objetivo de encontrar su relación en la tolerancia al Al en B. decumbens y B. brizantha y poder contribuir a una mejor comprensión de la hiperresistencia al Al en B. decumbens. Los compuestos fenólicos cambian en la presencia toxicidad por Al. En el último capítulo se estudiaran los cambios producidos por el aluminio a nivel de prteinas en la especie B. decumbens. Fue llevado a cabo este análisis por una moderna técnica 2-D-DIGE y análisis MALDI-TOF. Fueron identificadas 11 proteínas que fueron up y down-regulate durante la exposición al aluminio a las horas 96h. La cantidad de PAL (fenilalanina-amoniao-liasa) fue down-regulate después de 24h de exposición al aluminio, pero este se recupera casi a los niveles del control a 96h. / This thesis considers the differential responses to Al toxicity of three contrasting Brachiaria species in order to contribute to a better understanding of the Al resistance mechanisms in these economically important fodder grasses. The research was divided into 5 chapters. In the first one, we evaluated the response of three Brachiaria species to aluminium toxicity. Brachiaria decumbens, B. brizantha and B. ruziziensis were grown in low ionic strength nutrient solution and pH acid. Root elongation and the ability to maintain adequate nutrient homeostasis under Al stress was evaluated by mineral analysis of roots. In the second chapter we used different staining methods to analyse toxic effects and distribution of Aluminium in the root apex of the Brachiaria species. Localization of Al in Brachiaria roots was performed using confocal fluorescence microscopy of lumogallion or morin stained roots. In B. decumbens more efficiently excluded Al from the roots and in this species Al was localized mainly in root hair initials that developed close to the apex. These sites with high Al accumulation seem to contribute to low Al accumulation in sensitive root zones. In the third chapter Al-induced alterations on root surface structure of two Brachiaria species were observed. SEM-EDX and TEM techniques were used for better characterizing the time dependent responses to Al in B. decumbens and B. brizantha. We found that Al induced structural and ultrastructural alterations in both Brachiaria species. However, in the Al resistant B. decumbens root recovered after 96 h exposure to Al. These results indicate the inducible character of the Al tolerance mechanism in B. decumbens In the fourth chapter we explored the possible implication of phenolic substances in the differential Al tolerance of B. decumbens and B. brizantha in order to contribute to a better understanding of this hyperresistance to Al in B. decumbens. The phenolics change in the presence of Al-toxicity. Once characterize the most Al tolerant species (B. decumbens) in the last chapter the proteomic study was focused on this species. We conducted proteomic analysis of B. decumbens roots under Al stress after different exposure two times using 2-D-DIGE and MALDI-TOF analysis. A relative small number of only 11 proteins were found to be specifically up or down regulated during the first 96h of exposure to Al. Among those PAL (phenylalanine ammonia lyase) was found to be down regulated after 24 h exposure to Al, but recovered after 96 h.

The microstructural evolution and mechanical properties at elevated temperatures of a recently fabricated fine-grained AA6xxx aluminium sheet were evaluated and compared to the commercially fabricated sheet of the same alloy in the T4P condition. The behaviour of the fine-grained and T4P sheets was compared at elevated temperatures between 350°C and 550°C, as well as room temperature. Static exposure to elevated temperatures revealed that the precipitate structure of the fine-grained material did not change extensively. The T4P material, however, underwent extensive growth of precipitates, including a large amount of grain boundary precipitation. At room temperature, the T4P material deformed at much higher stresses than the FG material, but achieved lower elongations. Deformation at elevated temperatures revealed that the fine-grained material achieved significantly larger elongations to failure than the T4P material in the temperature range of 350°C-450°C. Both materials behaved similarly at 500°C and 550°C. Above 500°C, the grain size was greatly reduced in the T4P material, and only a slightly increased in the fine-grained material. At temperatures above 450°C, the elongation to failure in both materials generally increased with increasing strain-rate. The poor performance of the T4P material at low temperatures was attributed to the precipitate characteristics of the sheet, which lead to elevated stresses and increased cavitation. The deformation mechanism of both materials was found to be controlled by dislocation climb, accommodated by the self diffusion of aluminium at 500°C and 550°C. The deformation mechanism in the fine-grained material transitioned to power law breakdown at lower temperatures. At 350°C to 450°C, the T4P material behaved similarly to a particle hardened material with an internal stress created by the precipitates. The reduction in grain size of the T4P material after deformation at 500°C and 550°C was suggested to be caused by dynamic recovery/recrystallization. The role of a finer grain-size in the deformation behaviour at elevated temperatures was mainly related to enhanced diffusion through grain boundaries. The differences in the behaviour of the two materials were mainly attributed to the difference in the precipitation characteristics of the materials.

No description available.

The microstructural evolution and mechanical properties at elevated temperatures of a recently fabricated fine-grained AA6xxx aluminium sheet were evaluated and compared to the commercially fabricated sheet of the same alloy in the T4P condition. The behaviour of the fine-grained and T4P sheets was compared at elevated temperatures between 350°C and 550°C, as well as room temperature. Static exposure to elevated temperatures revealed that the precipitate structure of the fine-grained material did not change extensively. The T4P material, however, underwent extensive growth of precipitates, including a large amount of grain boundary precipitation. At room temperature, the T4P material deformed at much higher stresses than the FG material, but achieved lower elongations. Deformation at elevated temperatures revealed that the fine-grained material achieved significantly larger elongations to failure than the T4P material in the temperature range of 350°C-450°C. Both materials behaved similarly at 500°C and 550°C. Above 500°C, the grain size was greatly reduced in the T4P material, and only a slightly increased in the fine-grained material. At temperatures above 450°C, the elongation to failure in both materials generally increased with increasing strain-rate. The poor performance of the T4P material at low temperatures was attributed to the precipitate characteristics of the sheet, which lead to elevated stresses and increased cavitation. The deformation mechanism of both materials was found to be controlled by dislocation climb, accommodated by the self diffusion of aluminium at 500°C and 550°C. The deformation mechanism in the fine-grained material transitioned to power law breakdown at lower temperatures. At 350°C to 450°C, the T4P material behaved similarly to a particle hardened material with an internal stress created by the precipitates. The reduction in grain size of the T4P material after deformation at 500°C and 550°C was suggested to be caused by dynamic recovery/recrystallization. The role of a finer grain-size in the deformation behaviour at elevated temperatures was mainly related to enhanced diffusion through grain boundaries. The differences in the behaviour of the two materials were mainly attributed to the difference in the precipitation characteristics of the materials.