Corrosion

Summary

Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engineering is the field dedicated to controlling and preventing corrosion. In the most common use of the word, this means electrochemical oxidation of metal in reaction with an oxidant such as oxygen, hydrogen or hydroxide. Rusting, the formation of iron oxides, is a well-known example of electrochemical corrosion. This type of damage typically produces oxide(s) or salt(s) of the original metal and results in a distinctive orange coloration. Corrosion can also occur in materials other than metals, such as ceramics or polymers, although in this context, the term "degradation" is more common. Corrosion degrades the useful properties of materials and structures including mechanical strength, appearance, and permeability to liquids and gases. Many struc

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https://en.wikipedia.org/wiki/Corrosion

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Diamond-like carbon (DLC) coatings can improve the wear resistance of articulating implants. However despite successful in-vitro testing, some DLC coated joint replacements had to be revised prematurely, mainly due to coating delamination induced by corrosion at the substrate/DLC interface. Body fluid will enter defective coating sites and if the reactively formed interface or interlayer materials are instable in the confined fluid, they with dissolve, resulting in delamination of the DLC and ultimate failure of the implant. The aim of this thesis is therefore to investigate the corrosion mechanisms responsible for delamination at a substrate/DLC interface in body-like media. This is achieved by developing and implementing experimental methodologies addressing/simulating aggravating factors such as confinements/crevices, galvanic coupling, stress and fatigue on the interface to investigate corrosion initiation, propagation, and failure. Firstly, corrosion initiation and galvanic coupling risk are addressed with a methodology for accessing and characterizing the reactivity of buried interlayers. The interlayer is revealed by ion beam polishing, forming a wedge-like profile of the substrate/interlayer/DLC. The composition and chemical state of the interlayer/interface is determined by Auger electron spectroscopy. Reactive interlayers/interfaces, Si, titanium (Ti) and chromium (Cr), formed new phases (carbides and oxides). These new materials are then characterized with a local-electrochemical microcapillary technique. Cr and Si-DLC based interlayers presented good passive behavior, while a Si interlayer corroded in bovine-based wear test fluid (HyClone® WTF). The influence of coating defects on the current response of DLC surfaces was also investigated by varying the exposed working area (cm2 to µm2 range). To address the failure case of a TiAlV/Si/DLC implant, the influence of confinements/crevices on corrosion propagation is investigated. It is shown that Si is highly vulnerable to corrosion in confined conditions. Pitting corrosion susceptibility is found in a crevice, whereas a Si dissolution rate of ca. 3.6 nm/h at 37 °C occurs within a confined area. The corrosion rates increased at elevated temperatures and yielded linear Arrhenius relations, with activation energies of 106 KJ/mol in phosphate buffered saline (PBS) and 109 KJ/mol in HyClone® WTF. Phosphorous species enhanced Si dissolution, while chlorides were not so influential. Galvanic coupling with Ti and applied stress further accelerated the Si dissolution. Finally, corrosion related fracture of a CoCrMo/DLC interface is investigated by applying static and cyclic load. A reciprocating sliding rig is utilized to determine the number of sliding cycles required for interface delamination to occur at a critical load, in PBS at 37 °C. The results followed a Wöhler curve relation. Small O2 contaminations (0.5 and 1.0%) at the interface adversely affected the CF behaviour by lowering the critical load and endurance limit. The fitted Wöhler curves could be extrapolated and were found to be in good agreement with long-term experimental results previously obtained on an implant in a spinal disk simulator.

EPFL2019

Modèle d'évolution de l'état des ponts-routes en béton

Guido Roelfstra

The management of existing road infrastructures is a multidisciplinary activity that involves structural engineering, material science, management, economics and ecology. The objective is to achieve maximum availability of road links at minimum societal costs. Recently, tools (Bridge Management Systems, BMSs) have been developed to help decision makers to determine the optimal management strategies within available resources. The condition development model is a key element of the BMSs. Currently this model is using empirical approach making use of data collected during inspections and is formulated with Markov chains. The assessment units are structural elements and these are classified into condition classes according to their visual appearance. The condition assessment is therefore rather subjective since no measurements are involved in it. Consequently, the condition development based on visual inspections will reflect this subjectivity. In order to improve the objectivity of condition forecasts physical and chemical phenomena governing deterioration has to be incorporated in the condition development model. Observations made on a bridge sample representative of the Swiss highway bridges showed that chloride-induced corrosion is the main deterioration mechanism. For this reason this research was focused upon modeling the chloride-induced corrosion. In this research, the condition development model is established, based physical and chemical phenomena involved in chloride induced corrosion. This analytical model is able to yield quantitative results on condition development. Accuracy and availability of input data govern the level of accuracy of such an analytical model. The existing knowledge on chloride induced corrosion and inspection techniques available on site are examined in order to develop a simple and reliable condition development model. Firstly, non-destructive testing methods are used in addition to visual observations, to determine quantitative values (permeability and thickness of the concrete cover) of parameters governing the segment deterioration. The structural elements are divided into areas i.e. segments where the parameters governing chloride-induced corrosion are assumed to be constant. It is proposed to divide structural elements into segments based on three concrete cover permeability classes, concrete cover thickness and three types of surface exposures to chloride contaminated water. Secondly, a chloride transport model is developed to simulate the real exposure of reinforcement to chloride contaminated water, taking into consideration the transport mechanisms of water and chloride ions. Simulations are performed for the various segment parameters that have been identified in the segmental approach. Thirdly, a relation is established between the free chloride ion content and the corrosion initiation probability. Using the results of the chloride transport model, the development of the corrosion initiation is determined for road bridges segments. An analysis is made to predict the corrosion initiation time of existing bridges as a function of their segment parameters (exposure and concrete cover permeability and thickness), but also to establish recommendations for the construction of new bridges. Fourthly, the corrosion rate i.e. loss of steel cross-section is then determined according to the concrete cover permeability and the exposure to chloride contaminated water. Fifthly, the results of the presented mode1 are mapped to conditions States as defined in the BMSs. Three degradation matrices (Markov chains) are determined, corresponding to three condition developments: favorable, normal and unfavorable. The three condition developments can be estimated for given quantitative values of the concrete cover permeability, thickness and surface exposure to chloride-contaminated water. In this way, the segment parameters may be used in BMSs to forecasts future condition of segments, elements and the whole structure. Finally the structural behaviour of the concrete road-bridges until failure is studied. The determinant failure scenarios are identified for each bridge type and a case study is performed on the sample representative for the Swiss highway bridges. For this purpose the determinant segments for the structural safety are identified. Additionally the required concrete cover depth for a service life of 50 and 100 years is expressed as a function of the permeability and the exposure to chloride contaminated water. This research outlines the need to measure the concrete cover permeability and thickness with non-destructive test methods as well as to determine the exposure to chloride contaminated water. These values are essential to predict the condition development of concrete road bridges.

EPFL2001

Growth and viability of microorganisms in bentonite and their potential activity in deep geological repository environments

Niels Burzan

Radioactive waste is among the most dangerous anthropogenic waste and its safe disposal is a challenging multi-generational task. Many nations have sought for the peaceful application of nuclear fission for the reliable production of electric energy to power their societies. The increasing volumes of radioactive waste generated are, however, proving an increasingly urgent problem to tackle. Deep geological disposal is deemed our best option for the safe long-term disposal of radioactive waste. Different host rocks are being considered for deep geological disposal, depending on the nation's geology. Switzerland favours the Opalinus Clay Formation due to its very low hydraulic conductivity and good radionuclide retention capabilities. Microorganisms in the deep subsurface are active and must be considered as their activity will influence a deep geological repository for radioactive waste. On one hand, the microorganism's activity represents a safety concern due to the possibility of enhanced corrosion, when considering the metallic waste canister encapsulating spent fuel from nuclear power plants. In other cases, however, they can contribute to the safety of a deep geological repository, when considering the gas balance of a Swiss low- and intermediate-level repository. Anoxic corrosion of metallic radioactive waste poses risks to the structural integrity of the host rock. Harnessing the activity of naturally occurring microorganisms at a safe distance from the waste itself can result in the net reduction of gases and thus their activity can be viewed as beneficial and worth exploring. In this thesis, both the positive and negative aspects of the microbial presence are explored. Wyoming bentonite is a back-fill material and an important engineered barrier system for spent nuclear fuel and high-level waste. Within the framework of an in-situ corrosion experiment, the presence and growth of microorganisms in Wyoming bentonite are investigated. The results show that the activity of corrosion enhancing sulfate-reducing bacteria in Wyoming bentonite is inhibited during the critical bentonite saturation phase but other microorganisms were able to grow. The second in-situ research project explores the potential implementation of a microbial gas sink, a natural biofilm composed of hydrogen-oxidizing sulfate-reducing bacteria and methanogenic archaea. Indeed, under the right conditions, a microbial gas sink can fulfil its intended design purposes and consume all hydrogen-gas evolving from the anoxic corrosion of the waste. This thesis contributes to our understanding of the near-field processes of a Swiss radioactive waste repository within the Opalinus Clay Formation through the contribution of experimental insight obtained under in-situ conditions.

EPFL2021