AN ENTROPIC THEORY OF DAMAGE WITH APPLICATIONS TO CORROSION-FATIGUE STRUCTURAL INTEGRITY ASSESSMENT

This dissertation demonstrates an explanation of damage and reliability of critical components and structures within the second law of thermodynamics. The approach relies on the fundamentals of irreversible thermodynamics, specifically the concept of entropy generation due to materials degradation as an index of damage. All failure mechanisms that cause degradation, damage accumulation and ultimate failure share a common feature, namely energy dissipation. Energy dissipation, as a fundamental measure for irreversibility in a thermodynamic treatment of non-equilibrium processes, leads to and can be expressed in terms of entropy generation. The dissertation proposes a theory of damage by relating entropy generation to energy dissipation via generalized thermodynamic forces and thermodynamic fluxes that formally describes the resulting damage. Following the proposed theory of entropic damage, an approach to reliability and integrity characterization based on thermodynamic entropy is discussed. It is shown that the variability in the amount of the thermodynamic-based damage and uncertainties about the parameters of a distribution model describing the variability, leads to a more consistent and broader definition of the well know time-to-failure distribution in reliability engineering. As such it has been shown that the reliability function can be derived from the thermodynamic laws rather than estimated from the observed failure histories. Furthermore, using the superior advantages of the use of entropy generation and accumulation as a damage index in comparison to common observable markers of damage such as crack size, a method is proposed to explain the prognostics and health management (PHM) in terms of the entropic damage. The proposed entropic-based damage theory to reliability and integrity is then demonstrated through experimental validation. Using this theorem, the corrosion-fatigue entropy generation function is derived, evaluated and employed for structural integrity, reliability assessment and remaining useful life (RUL) prediction of Aluminum 7075-T651 specimens tested.

Investigating wetting characteristics on microstructured surfaces for superhydrophobicity and metal microcasting

The engineering of liquid behavior on surfaces is important for infrastructure, transportation, manufacturing, and sensing. Surfaces can be rendered superhydrophobic by microstructuring, and superhydrophobic devices could lead to practical corrosion inhibition, self-cleaning, fluid flow control, and surface drag reduction. To more fully understand how liquid interacts with microstructured surfaces, this dissertation introduces a direct method for determining droplet solid-liquid-vapor interfacial geometry on microstructured surfaces. The technique performs metrology on molten metal droplets deposited onto microstructured surfaces and then frozen. Unlike other techniques, this visualization technique can be used on large areas of curved and opaque microstructured surfaces to determine contact line. This dissertation also presents measurements and models for how curvature and flexing of microstructured polymers affects hydrophobicity. Increasing curvature of microstructured surfaces leads to decreased slide angle for liquid droplets suspended on the surface asperities. For a surface with regularly spaced asperities, as curvature becomes more positive, droplets suspended on the tops of asperities are suspended on fewer asperities. Curvature affects superhydrophobicity because microscopic curvature changes solid-liquid interaction, pitch is altered, and curvature changes the shape of the three phase contact line. This dissertation presents a model of droplet interactions with curved microstructured surfaces that can be used to design microstructure geometries that maintain the suspension of a droplet when curved surfaces are covered with microstructured polymers. Controlling droplet dynamics could improve microfluidic devices and the shedding of liquids from expensive equipment, preventing corrosion and detrimental performance. This dissertation demonstrates redirection of dynamic droplet spray with anisotropic microstructures. Superhydrophobic microstructured surfaces can be economically fabricated using metal embossing masters, so this dissertation describes casting-based microfabrication of metal microstructures and nanostructures. Low melting temperature metal was cast into flexible silicone molds which were themselves cast from microfabricated silicon templates. The flexibility of the silicone mold permits casting of curved surfaces, which this dissertation demonstrates by fabricating a cylindrical metal roller with microstructures. The metal microstructures can be in turn used as a reusable molding tool. This dissertation also describes an industrial investment casting process to produce aluminum molds having integrated microstructures. Unlike conventional micromolding tools, the aluminum mold was large and had complex curved surfaces. The aluminum was cast into curved microstructured ceramic molds which were themselves cast from curved microstructured rubber. Many structures were successfully cast into the aluminum with excellent replication fidelity, including circular, square, and triangular holes. This dissertation demonstrates molding of large, curved surfaces having surface microstructures using the aluminum mold. This work contributes a more full understanding of the phenomenon of superhydrophobicity and techniques for the economic fabrication of superhydrophobic microstructures.

Aluminum and bone: Review of new clinical circumstances associated with Al(3+) deposition in the calcified matrix of bone

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Accelerated and natural carbonation of concretes with internal curing and shrinkage/viscosity modifiers

Abstract In many parts of the world, corrosion of reinforcing steel in concrete induced by carbonation of the concrete continues to be a major durability concern. This paper investigates the accelerated and natural carbonation resistance of a set of seven concretes, specifically evaluating the effects of internal curing and/or shrinkage/viscosity modifiers on carbonation resistance. In addition to five different ordinary portland cement (OPC) concretes, two concretes containing 20 % of a Class F fly ash as replacement for cement on a mass basis are also evaluated. For all seven concrete mixtures, a good correlation between accelerated (lab) and natural (field) measured carbonation coefficients is observed. Conversely, there is less correlation observed between the specimens’ carbonation resistance and their respective 28 days compressive strengths, with the mixtures containing the shrinkage/viscosity modifier specifically exhibiting an anomalous behavior of higher carbonation resistance at lower strength levels. For both the accelerated and natural exposures, the lowest carbonation coefficients are obtained for two mixtures, one containing the shrinkage/viscosity modifier added in the mixing water and the other containing a solution of the same admixture used to pre-wet fine lightweight aggregate. Additionally, the fly ash mixtures exhibited a significantly higher carbonation coefficient in both exposures than their corresponding OPC concretes.

Galvanic corrosion of two non noble dental alloys

Artigo licenciado sob uma Licença Creative Commons: https://creativecommons.org/licenses/by/4.0/

Dynamic mechanical-thermal, microstructural and mechanical analysis of ultra-light polymer-metal composites: influence of forming

A really particular and innovative metal-polymer sandwich material is Hybrix. Hybrix is a product developed and manufactured by Lamera AB, Gothenburg, Sweden. This innovative hybrid material is composed by two relatively thin metal layers if compared to the core thickness. The most used metals are aluminum and stainless steel and are separated by a core of nylon fibres oriented perpendicularly to the metal plates. The core is then completed by adhesive layers applied at the PA66-metal interface that once cured maintain the nylon fibres in position. This special material is very light and formable. Moreover Hybrix, depending on the specific metal which is used, can achieve a good corrosion resistance and it can be cut and punched easily. Hybrix architecture itself provides extremely good bending stiffness, damping properties, insulation capability, etc., which again, of course, change in magnitude depending in the metal alloy which is used, its thickness and core thickness. For these reasons nowadays it shows potential for all the applications which have the above mentioned characteristic as a requirement. Finally Hybrix can be processed with tools used in regular metal sheet industry and can be handled as solid metal sheets. In this master thesis project, pre-formed parts of Hybrix were studied and characterized. Previous work on Hybrix was focused on analyze its market potential and different adhesive to be used in the core. All the tests were carried out on flat unformed specimens. However, in order to have a complete description of this material also the effect of the forming process must be taken into account. Thus the main activities of the present master thesis are the following: Dynamic Mechanical-Thermal Analysis (DMTA) on unformed Hybrix samples of different thickness and on pre-strained Hybrix samples, pure epoxy adhesive samples analysis and finally moisture effects evaluation on Hybrix composite structure.

IMPROVED SAMPLE INTRODUCTION SYSTEMS FOR INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION SPECTROMETRY AND THEIR APPLICATION TO THE ANALYSIS OF SIMPLE AND COMPLEX MATRICES

The objective of this thesis is to explore new and improved methods for greater sample introduction efficiency and enhanced analytical performance with inductively coupled plasma optical emission spectrometry (ICP-OES). Three projects are discussed in which the capabilities and applications of ICP-OES are expanded: 1. In the first project, a conventional ultrasonic nebuliser was modified to replace the heater/condenser with an infrared heated pre-evaporation tube. In continuation from previous works with pre-evaporation, the current work investigated the effects of heating with infrared block and rope heaters on two different ICP-OES instruments. Comparisons were made between several methods and setups in which temperatures were varied. By monitoring changes to sensitivity, detection limit, precision, and robustness, and analyzing two certified reference materials, a method with improved sample introduction efficiency and comparable analytical performance to a previous method was established. 2. The second project involved improvements to a previous work in which a multimode sample introduction system (MSIS) was modified by inserting a pre-evaporation tube between the MSIS and torch. The new work focused on applying an infrared heated ceramic rope for pre-evaporation. This research was conducted in all three MSIS modes (nebulisation mode, hydride generation mode, and dual mode) and on two different ICP-OES instruments, and comparisons were made between conventional setups in terms of sensitivity, detection limit, precision, and robustness. By tracking both hydride-forming and non-hydride forming elements, the effects of heating in combination with hydride generation were probed. Finally, optimal methods were validated by analysis of two certified reference materials. 3. A final project was completed in collaboration with ZincNyx Energy Solutions. This project sought to develop a method for the overall analysis of a 12 M KOH zincate fuel, which is used in green energy backup systems. By employing various techniques including flow injection analysis and standard additions, a final procedure was formulated for the verification of K concentration, as well as the measurement of additives (Al, Fe, Mg, In, Si), corrosion products (such C from CO₃²¯), and Zn particles both in and filtered from solution. Furthermore, the effects of exposing the potassium zincate electrolyte fuel to air were assessed.

“Acid-spike” effect in spurs/tracks of the low/high linear energy transfer radiolysis of water : potential implications for radiobiology and nuclear industry

Résumé : Les ions hydronium (H3O + ) sont formés, à temps courts, dans les grappes ou le long des trajectoires de la radiolyse de l'eau par des rayonnements ionisants à faible transfert d’énergie linéaire (TEL) ou à TEL élevé. Cette formation in situ de H3O + rend la région des grappes/trajectoires du rayonnement temporairement plus acide que le milieu environnant. Bien que des preuves expérimentales de l’acidité d’une grappe aient déjà été signalées, il n'y a que des informations fragmentaires quant à son ampleur et sa dépendance en temps. Dans ce travail, nous déterminons les concentrations en H3O + et les valeurs de pH correspondantes en fonction du temps à partir des rendements de H3O + calculés à l’aide de simulations Monte Carlo de la chimie intervenant dans les trajectoires. Quatre ions incidents de différents TEL ont été sélectionnés et deux modèles de grappe/trajectoire ont été utilisés : 1) un modèle de grappe isolée "sphérique" (faible TEL) et 2) un modèle de trajectoire "cylindrique" (TEL élevé). Dans tous les cas étudiés, un effet de pH acide brusque transitoire, que nous appelons un effet de "pic acide", est observé immédiatement après l’irradiation. Cet effet ne semble pas avoir été exploré dans l'eau ou un milieu cellulaire soumis à un rayonnement ionisant, en particulier à haut TEL. À cet égard, ce travail soulève des questions sur les implications possibles de cet effet en radiobiologie, dont certaines sont évoquées brièvement. Nos calculs ont ensuite été étendus à l’étude de l'influence de la température, de 25 à 350 °C, sur la formation in situ d’ions H3O + et l’effet de pic acide qui intervient à temps courts lors de la radiolyse de l’eau à faible TEL. Les résultats montrent une augmentation marquée de la réponse de pic acide à hautes températures. Comme de nombreux processus intervenant dans le cœur d’un réacteur nucléaire refroidi à l'eau dépendent de façon critique du pH, la question ici est de savoir si ces fortes variations d’acidité, même si elles sont hautement localisées et transitoires, contribuent à la corrosion et l’endommagement des matériaux.

On the Chemical Signature and Origin of Dicoppertrihydroxyformate (Cu2(OH)3HCOO) Formed on Copper Miniatures of 17th and 18th centuries

A corrosion product rarely reported in the literature has been found on the copper support of three miniature paintings of the 17th and 18th centuries. This product, which has been identified as dicoppertrihydroxyformate (Cu2(OH)3HCOO), is an unusual basic copper formate found on copper artifacts. The identification and characterization of dicoppertrihydroxyformate was carried out directly over the corroded surface of the objects, using a nondestructive approach, which combines the integrated use of various microanalytical techniques. Using this approach, it was possible to obtain a set of new reference data about the natural form of Cu2(OH)3HCOO, that will enable its unambiguous identification in other similar objects. In this work, the probable causes that may have contributed to its formation are also discussed.

Development and optimisation of protocols for surface cleaning of cultural heritage metals

The conservation and valorisation of cultural heritage is of fundamental importance for our society, since it is witness to the legacies of human societies. In the case of metallic artefacts, because corrosion is a never-ending problem, the correct strategies for their cleaning and preservation must be chosen. Thus, the aim of this project was the development of protocols for cleaning archaeological copper artefacts by laser and plasma cleaning, since they allow the treatment of artefacts in a controlled and selective manner. Additionally, electrochemical characterisation of the artificial patinas was performed in order to obtain information on the protective properties of the corrosion layers. Reference copper samples with different artificial corrosion layers were used to evaluate the tested parameters. Laser cleaning tests resulted in partial removal of the corrosion products, but the lasermaterial interactions resulted in melting of the desired corrosion layers. The main obstacle for this process is that the materials that must be preserved show lower ablation thresholds than the undesired layers, which makes the proper elimination of dangerous corrosion products very difficult without damaging the artefacts. Different protocols should be developed for different patinas, and real artefacts should be characterised previous to any treatment to determine the best course of action. Low pressure hydrogen plasma cleaning treatments were performed on two kinds of patinas. In both cases the corrosion layers were partially removed. The total removal of the undesired corrosion products can probably be achieved by increasing the treatment time or applied power, or increasing the hydrogen pressure. Since the process is non-invasive and does not modify the bulk material, modifying the cleaning parameters is easy. EIS measurements show that, for the artificial patinas, the impedance increases while the patina is growing on the surface and then drops, probably due to diffusion reactions and a slow dissolution of copper. It appears from these results that the dissolution of copper is heavily influenced by diffusion phenomena and the corrosion product film porosity. Both techniques show good results for cleaning, as long as the proper parameters are used. These depend on the nature of the artefact and the corrosion layers that are found on its surface.

Accelerated ageing methodologies for the evaluation of particulate matter role in the corrosion of outdoor-exposed bronzes

Deterioration phenomena occurring on outdoor cultural heritage have been the subject of several studies, but relatively few works investigated the specific role of Particulate Matter (PM) in the corrosion of metals. This topic is really complex and, besides field exposures, accelerated ageing tests are also necessary to isolate and understand deterioration mechanisms due to PM. For this reason, the development of a methodology that allows to reproduce and analyze the effect of PM on alloys through accelerated ageing in climatic chamber has been started. On quaternary bronze specimens, single salts and a mix of them were deposited via two deposition methods: dry (directly depositing the salt on the surface) and wet (dropping a salt solution and drying it), simulating the initial chemical activation of the salts by RH% variations or by raindrops, respectively. Then, to better mimic the composition of real PM, a mixture containing a soluble salts, a mineral, a black carbon and an organic fraction was formulated and spread on the samples. The samples were placed in a climatic chamber and exposed to cyclic variations of T and RH for three weeks. The ageing cycles were set according to predictions on salt deliquescence/recrystallization through E-AIM model and to the evaluation of regional climatic data. The surface evolution was followed by SEM-EDX, Raman, AT-IR and UV-Vis Spectrophotometry. At the end of the test, mass losses were determined and corroded metals removed by pickling were analyzed by AAS. On the basis of the obtained results, the tested procedures seem to be promising in accelerating and mimicking realistic corrosion phenomena, as under the selected conditions, corrosion products typically found at different exposure time (from days to years) on outdoor bronzes were able to progressively form and evolve. Moreover, the two deposition modes simulating different condition of chemical activation of PM deposits allow to obtain complementary information.

Strength and ductility of corroded strands within the framework of safety assessment of existing bridges

Existing bridges built in the last 50 years face challenges due to states far different than those envisaged when they were designed, due to increased loads, ageing of materials, and poor maintenance. For post-tensioned bridges, the need emerged for reliable engineering tools for the evaluation of their capacity in case of steel corrosion due to lack of mortar injection. This can lead to sudden brittle collapses, highlighting the need for proper maintenance and monitoring. This thesis proposes a peak strength model for corroded strands, introducing a “group coefficient” that aims at considering corrosion variability in the wires constituting the strands. The application of the introduced model in a deterministic approach leads to the proposal of strength curves for corroded strands, which represent useful engineering tools for estimating their maximum strength considering both geometry of the corrosion and steel material parameters. Together with the proposed ultimate displacement curves, constitutive laws of the steel material reduced by the effects of corrosion can be obtained. The effects of corroded strands on post-tensioned beams can be evaluated through the reduced bending moment-curvature diagram accounting for these reduced stress-strain relationships. The application of the introduced model in a probabilistic approach allows to estimate peak strength probability functions and consecutive design-oriented safety factors to consider corrosion effects in safety assessment verifications. Both approaches consider two procedures that are based on the knowledge level of the corrosion in the strands. On the sidelines of this main research line, this thesis also presents a study of a seismic upgrading intervention of a case-study bridge through HDRB isolators providing a simplified procedure for the identification of the correct device. The study also investigates the effects due to the variability of the shear modulus of the rubber material of the HDRB isolators on the structural response of the isolated bridge.

Numerical modeling and experimental validation of the recrystallization behaviour in the extrusion of 6XXX aluminum alloys

The microstructure of 6XXX aluminum alloys deeply affects mechanical, crash, corrosion and aesthetic properties of extruded profiles. Unfortunately, grain structure evolution during manufacturing processes is a complex phenomenon because several process and material parameters such as alloy chemical composition, temperature, extrusion speed, tools geometries, quenching and thermal treatment parameters affect the grain evolution during the manufacturing process. The aim of the present PhD thesis was the analysis of the recrystallization kinetics during the hot extrusion of 6XXX aluminum alloys and the development of reliable recrystallization models to be used in FEM codes for the microstructure prediction at a die design stage. Experimental activities have been carried out in order to acquire data for the recrystallization models development, validation and also to investigate the effect of process parameters and die design on the microstructure of the final component. The experimental campaign reported in this thesis involved the extrusion of AA6063, AA6060 and AA6082 profiles with different process parameters in order to provide a reliable amount of data for the models validation. A particular focus was made to investigate the PCG defect evolution during the extrusion of medium-strength alloys such as AA6082. Several die designs and process conditions were analysed in order to understand the influence of each of them on the recrystallization behaviour of the investigated alloy. From the numerical point of view, innovative models for the microstructure prediction were developed and validated over the extrusion of industrial-scale profiles with complex geometries, showing a good matching in terms of the grain size and surface recrystallization prediction. The achieved results suggest the reliability of the developed models and their application in the industrial field for process and material properties optimization at a die-design stage.