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This thesis describes the metallurgical and environmental factors that influence hydrogen embrittlement of super duplex stainless steels and presents a model to predict the rate at which embrittlement occurs. Super duplex stainless steel has an austenite and ferrite microstructure with an average fraction of each phase of approximately 50%. An investigation was carried out on the metallurgical and environmental factors that influence hydrogen embrittlement of super duplex stainless steels. Tensile specimens of super duplex stainless steel were pre-charged with hydrogen for two weeks in 3.5% NaCl solution at 50º C at a range of applied potentials to simulate the conditions that exist when subsea oilfield components are cathodically protected in seawater. The pre-charged specimens were then tested in a slow strain rate tensile test and their susceptibility to hydrogen embrittlement was assessed by the failure time, reduction in cross-sectional area and examination of the fracture surface. The ferrite and austenite in the duplex microstructures were identified by analysing their Cr, Ni, Mo and N contents in an electron microscope, as these elements partition in different concentrations in the two phases. It was shown that hydrogen embrittlement occurred in the ferrite phase, whereas the austenite failed in a ductile manner. An embrittled region existed around the circumference of each fracture surface and the depth of this embrittlement depended on the hydrogen charging time and the potential at which the charging had been carried out. The depth of embrittlement was shown to correlate with the rate of hydrogen diffusion in the alloy, which was measured electrochemically using hydrogen permeation and galvanostatic methods. A two-dimensional diffusion model was used to calculate the hydrogen distribution profiles for each experimental condition and the model could be employed to provide predictions of expected failure times in stressed engineering components.

Un nouveau procédé, basé sur une adaptation innovante du principe de protection cathodique des ouvrages métalliques en milieu marin, consiste à favoriser la précipitation d’un agglomérat calcomagnésien sur plusieurs centimètres d’épaisseur. En présence de sable et de coquillages, cet agglomérat pourrait permettre de stabiliser des zones littorales en cours d’érosion ou d’améliorer l’ancrage d’enrochements brise-lames. L’objectif de ce travail est d’étudier et de comprendre les mécanismes réactionnels de formation de cet agglomérat permettant une précipitation en volume loin de la cathode afin d’en optimiser la vitesse de formation ainsi que ses propriétés mécaniques. Premièrement, il a été montré dans ces travaux que le milieu électrolytique pouvait influer sur la croissance du dépôt, avec une possible inhibition de formation de carbonate de calcium pour les faibles potentiels. L’influence des produits de corrosion dans le mécanisme de protection cathodique a également été mise en évidence grâce à des polarisations effectuées dans NaCl, eau de mer artificielle et naturelle. Deuxièmement, des essais d’un mois en courant imposé ont été menés du laboratoire jusqu’au site naturel, afin de se rapprocher des conditions réelles. La densité de courant appliquée ainsi que les conditions hydrodynamiques sont des facteurs clefs étroitement liés l’un à l’autre, influant sur la masse et le rapport Ca/Mg. Ces travaux ont aussi permis de mettre en avant l’influence du temps de polarisation sur la composition du dépôt calcomagnésien, présentant une cinétique de croissance stable mais une fluctuation de composition après 15, 30 et 60 jours. Cette variation interne du rapport Ca/Mg, attribuée à un processus de « dissolution/précipitation » dépendant du gradient de pH, ainsi que la répartition de ces éléments au sein du dépôt pourraient jouer un rôle majeur dans l’évolution de la tenue mécanique du dépôt au cours du temps. / A new method, based on an innovative adaptation of cathodic protection principle of metal structures in marine environment, is to promote the precipitation of a calcareous agglomerate several centimeters thick. In the presence of sand and shells, this cluster could stabilize coastal areas being eroded or improve anchorage of breakwater riprap. The objective of this work is to study and understand the reaction mechanisms allowing to create a voluminous calcareous deposit away from the cathode and to optimize deposition time as well as its mechanical properties. First, it was shown in this work that the electrolytic medium could affect the growth of the deposit, with a possible inhibition of formation of calcium carbonate fot the low potential. The influence of corrosion products in the cathodic protection mechanism was also highlighted through polarizations performed in NaCl, artificial and natural sea water. Second, one month test with impressed current were conducted from laboratory to natural site, in order to get closer of real conditions. Current density and hydrodynamic conditions are key factors closely bonded to each other, affecting the mass and composition of the Ca/Mg ratio. This work has also helped to highlight the influence of the polarization time on the composition, with stable growth kinetics but a composition’s evolution after 15, 30 and 60 days. This internal variation of the Ca/Mg ratio attributed to a process of « dissolution/precipitation » is pH dependent and the distribution of these elements within the deposit could play a major role in the evolution of the mechanical strength of deposit over time.

La protection cathodique par courant imposé (PCCI) est l’une des techniques adoptées pour limiter ou annihiler la corrosion dans le béton armé. Le but de cette thèse est de développer des revêtements suffisamment conducteurs et autonomes pour s’affranchir de l’utilisation des anodes primaires métalliques lors de la PCCI. Ce mémoire est formé de quatre parties principales :I. La première partie résume la recherche bibliographique réalisée. II. Cette partie sera consacrée à la formulation des revêtements électro-conducteurs par dispersion des poudres-pigmentaires conductrices (métallique ou carbone) dans une résine acrylique ou polyuréthane. III. L’efficacité des revêtements électro-conducteurs en tant qu’anode autonome est étudiée dans cette partie. IV. La dernière partie présente des essais de PCCI réalisés en continu pendant 6 mois sur des dallettes corrodées. Des spécimens témoins non corrodés sont aussi placés dans le même environnement sans protection cathodique. / Impressed Current Cathodic Protection (ICPP) is one of the electrochemical techniques applied to limit or annihilate corrosion. The aim of this thesis is to develop sufficiently conductive and autonomous coatings to overcome the use of primary anodes during ICPP. This thesis is based on four main parts:I. The first part summarizes a bibliographic review of corrosion in reinforced concrete. II. This part will focus on the formulation of electroconductive coatings by mixing conductive powders (metallic or carbon) with an acrylic or polyurethane resin. III. The effectiveness of electroconductive coatings as an autonomous anode is studied in this section. IV. The last part presents ICCP tests carried out continuously for 6 months on corroded slabs. Non-corroded specimens are also placed in the same environment without cathodic protection in order to make a comparative analysis.

Ett stort industriellt problem när det gäller metalliska material är korrosion. En metod för att förhindra korrosion är genom en elektrokemisk process som kallas katodiskt skydd vilket kan utföras på två olika sätt: Katodiskt korrosionsskydd med påtryckt ström (ICCP) eller offeranod (SACP). SACP är baserat på oxidation av de mindre ädla metalliska offeranoderna som vanligtvis är gjorda av zink- och aluminiumlegeringar. Det finns ett stort behov av att forska på andra alternativ för dessa anoder eftersom metallerna som används vis SACP släpper ut tungmetaller i havsvatten. Ledande polymerer (CP) har intressanta och kontrollerande elektriska och elektrokemiska egenskaper vilket gör dem till ett miljövänligt alternativ vid val av anod för SACP.  I följande studie var de utvalda ledande polymererna poly(3,4-etylendioxytiopend)polystyrensulfat (PEDOT:PSS) och polypyrrole-SDS (PPy-SDS). PEDOT:PSS syntetiserades och PPy-SDS köptes. Deras beteende i artificiellt havsvatten analyserades I syfte att bestämma utvecklingen av polymerstrukturen och egenskaper samt eventuella förändringar i havsvattenegenskaperna. Inga av dessa polymerer visade förändringar i den molekylära strukturen till skillnad från den kristallinga strukturen som påverkades. Dessutom släppte inte PPy-SDS ut och komponenter i vattnet till skillnad från PEDOT:PSS som genomgick mekanisk sönderfall vid kontakt med konstgjort havsvatten.  För att förbättra konduktiviteten, post-dopning med metanol och svavelsyra utfördes på PEDOT:PSS vilket inte var fallet när post-dopning med metanol utfördes, det var dock inte möjligt att få en konduktivitet av PEDOT:PSS post-doped  med svavelsyra.  Elektrod tillverkningsmetod utfördes och undersöktes i denna studie. Metoderna inkluderade komprimering från 3000bar till 6000bar vid olika temperaturer och olika geometrier av elektrod. Temperaturen hade en positiv effekt på polymerernas ledningsförmåga. / A major industrial issue when it comes to metallic materials is corrosion. One method to prevent corrosion to occur is by an electrochemical process called cathodic protection which is done in two different ways: impressed current cathodic protection (ICCP) or sacrificial anode cathodic protection (SACP). SACP is based on oxidation of the less noble metal which usually is made of zinc and aluminum alloys. The environmental concerns of these anodes due to the release of heavy metals in the seawater induced a strong need to explore other alternatives. Then, conductive polymers (CP) with their interesting and controllable electrical and electrochemical properties represent an opportunity to investigate as an eco-friendly anodic material.  In the following study, two conductive polymers were chosen: poly(3,4-ethylenedioxythiopende)polystyrene sulfonate (PEDOT:PSS) and polypyrrole-SDS (PPy-SDS). The former was synthesized, while the latter was purchased. Their behavior as polymer powders in artificial seawater was analyzed with the aim to determine the evolution of polymer structure and properties as well as any change in the seawater characteristics. Neither of these polymers showed changes in the molecular structure contrary to the crystalline structure which was affected. Furthermore, PPy-SDS did not release any components to the water unlike PEDOT:PSS which went through mechanical disintegration when in contact with artificial seawater.  To improve the conductivity of PEDOT:PSS post-doping with methanol and sulfuric acid were performed. The obtained results did not show the expected effect which need further optimization of post-doping conditions.  Electrode fabrication method was proposed and investigated in this study. The methods included compression from 3000bar to 6000bar at different temperatures and different geometries of electrode. The temperature had a positive effect on the conductivity of the polymers without an impact on their structure.

Through history, iron has mainly been used as reinforcement in concrete. Contemporary building technology would not have been possible without reinforced concrete, however, from a global perspective, many concrete buildings have begun to encounter reinforcement corrosion, mainly due to chlorides and carbonation. When the chlorides come into contact with the reinforcing bars, a chemical reaction begins, which causes the iron to oxidize and begin to corrode. In a humid environment when the reinforcement corrodes, the iron expands and bursts the concrete from inside, which in turn results in cracks occurring in the concrete structure. In an environment with lack of oxygen, it often occurs that non expanding rust products form that are not defected on the concrete surface occurs through discoloring or spalling. This type of damage is not detected ocularly and therefore forms a more serious type of injury. This type of rust is a silent type of damage that can cause deteriorated bearing capacity in the construction, since the cross-sectional area of the reinforcement in the concrete decreases. Sweco has been involved in a couple of projects where there have been huge problems due to corrosion of reinforcement. The damages that emerged leading to the repairs of these type of damage costing large sums. This report is based on previous projects, articles, literature studies, reports and interviews. Interviews have been conducted with competent people who have shared their valuable opinions, knowledge and experiences. In order to stop ongoing corrosion of reinforcement and also repair the damage, several alternative solution and repair measures have been devolped. Some of the most relevant suggestions in this report is to remove the damaged concrete and then re-cast or alternatively cast in cathodic protection or a combination of these. / Genom historien har man främst använt sig av järn som armering i betong. Samtidens byggteknik hade inte varit möjlig utan armerad betong, dock behöver man vara uppmärksam på armeringskorrosion framför allt på grund av klorider och karbonatisering. När kloriderna kommer i kontakt med armeringsjärnen påbörjas en kemisk reaktion som leder till att järnen oxiderar och börjar korrodera. I fuktig miljö när armeringen korroderar, expanderar järnen och spränger betongen inifrån vilket i sin tur resulterar i att sprickor uppstår i betongkonstruktionen. I syrefattiga miljöer uppstår det oftast svartrost som är den typ av skada som uppstår inuti en betongkonstruktion. Denna typ av skada upptäcks inte okulärt och blir därför en allvarligare typ av skada. Svartrost är även den typ av skada som kan förorsaka försämrad bärighet i konstruktionen eftersom tvärsnittsarean hos armeringen i betongen minskar. Sweco har varit inblandade i ett par projekt där det har förekommit enorma problem på grund av armeringskorrosion. Skadorna som har uppstått på grund av armeringskorrosion har lett till att reparationerna av dessa skador har varit kostsamma. Denna rapport är baserad på tidigare projekt, artiklar, litteraturstudier, rapporter samt intervjuer. Intervjuer har genomförts med kompetenta personer som har delat med sig av sina värdefulla åsikter, kunskaper och erfarenheter för att få en bättre uppfattning av konsekvenserna som uppstår på grund av armeringskorrosion. För att stoppa pågående armeringskorrosion och även reparera skadorna, har reparationsåtgärder i denna rapport tagits fram. Några utav de mest relevanta förslag på åtgärder i denna rapport är att ta bort den skadade betongen för att sedan gjuta på nytt, alternativt gjuta in katodiskt skydd eller en kombination av dessa.

[pt] A corrosão é a patologia mais recorrente no concreto armado, responsável por custos elevados na recuperação das estruturas afetadas. Além dos custos diretos como os materiais utilizados na recuperação, a mão de obra especializada, substituição de peças ou equipamentos afetados, existem os custos indiretos como a paralização da utilização da estrutura, mobilização de moradores em caso de edificações residenciais, perda de produção em caso de edificação industriais, entre outros. Encontrar e apresentar meios para o combate e a prevenção da corrosão é de extrema importância. A proteção catódica tem se apresentado nas últimas décadas como uma forma eficaz de combate a corrosão, não só paralisando o processo corrosivo totalmente, mas também prevenindo o surgimento de novos pontos. Seu uso vem sendo aplicado cada vez mais em estruturas de concreto armado, como pontes, cais, edifícios industriais e residenciais e túneis. Diversos materiais vêm sendo testados e aprovados, possibilitando a flexibilização e a adaptação do melhor sistema para cada estrutura. Relatos de casos com uso da proteção catódica tem mostrado a sua eficácia mesmo depois de anos de instalação. Essa dissertação apresenta a proteção catódica, seus sistemas de uso, casos em que foi instalada, um experimento com proteção catódica por corrente impressa para a restauração de uma ferramenta de aço, além de um modelo computacional desenvolvido para o dimensionamento de anodos galvânicos para estruturas de concreto armado. / [en] Corrosion is the most recurrent pathology in reinforced concrete, responsible for high costs in the recovery of affected structures. In addition to direct costs such as materials used in the recovery, specialized labor, replacement of affected parts or equipment, there are indirect costs such as the interruption of use of the structure, mobilization of residents in case of residential buildings, loss of production in case of industrial buildings, among others. Finding and introducing means to combat and prevent corrosion is extremely important. Cathodic protection has been presented in the last decades as an effective way to combat the corrosion, as it not only paralyzes the corrosive process completely, but also preventing the combat to new points. Its use has been increasingly applied in structures such as bridges, industrial and residential buildings, and tunnels. Various materials have been tested and approved, adaptation system for flexibility and adaptation to better each structure. Case reports with the use of cathodic protection have had attention even after years of installation. This dissertation presents cathodic protection, its systems of use, cases in which it was installed, an experiment with cathodic protection by impressed current for the restoration of a steel tool, as well as a computational model developed for the design of galvanic anodes for reinforced concrete structures.

Galvanic anode technology has in recent years come to the fore as a cost-effective method of successfully mitigating the corrosion of reinforcing steel in concrete structures. Developments in the field of cathodic protection have included the introduction of a novel Hybrid anode system, which uses the same sacrificial anode to pass a short-term impressed current before being connected to the steel directly to provide a long-term galvanic current. Galvanic and hybrid technologies are often seen as less powerful solutions in the treatment of reinforcement corrosion, and the test methodologies which determine the efficacy of cathodic protection systems favour impressed current technologies. The work completed has investigated the application of traditional and novel corrosion assessment techniques to laboratory samples to assess the protection offered by the hybrid treatment methodology in both treatment phases. In addition, the response of both galvanic and hybrid anodes to environmental conditions has been recorded and assessed before being discussed in the context of steel protection criteria. Finally, an investigation is presented into the on-site deterioration of commercially pure titanium feeder wire installed as part of the hybrid anode system and potential solutions to the problem have been documented. The research undertaken found that the hybrid anode system is capable of protecting steel in challenging, aggressive environments. This was confirmed by steel corrosion rate and indicative steel potential measurements. The responsive behaviour investigation showed that the current output of galvanic and hybrid anodes responds rapidly to changes in the corrosion risk posed to the steel and that this has a direct effect on anode system lifetimes. An assessment of the polarisation-based protection criteria applied to steel in concrete has found that the standard inhibits the use of responsive behaviour, and that revisions which consider the present risk of steel corrosion by considering the corrosion current resulting from the relative aggressivity of the concrete environment would be more valid in their application. A cathodic protection system based on the concepts of pit re-alkalisation and pH maintenance can fully utilise galvanic anode responsive behaviour. It was discovered that the deterioration of commercially pure titanium feeder wire seen on site installations was due to anodising in the presence of chloride media which had the potential to lead to pitting corrosion. The pitting risk varied depending on the duration of the treatment and proximity to the installed anode. An anodically grown oxide delayed the onset of corrosion in aqueous KBr solution, but did not significantly increase the pitting potential.

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