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- 7.6 Korrosion und Korrosionsschutz (15) (entfernen)
The corrosion of steel in reinforced concrete structures is one of the main threats to their durability. Based on the scientific achievements of the past decades the knowledge about the deterioration mechanisms and possible repair strategies for corrosion induced damages have found their way into practice.
It is common sense, that a detailed assessment of the structure is the foundation for a successful repair measure. In addition to the “traditional” singular on-site-procedures such as measurement of concrete cover, carbonation depth, half-cell potentials and chloride contents the monitoring of corrosion related parameters has gained in importance over the past few years.
The advantages of a corrosion monitoring are obvious. In new buildings, structural elements which cannot be assessed after completion (e.g. tunnel segments), or members with electrically isolating coatings can be monitored by means of integrated sensors providing an insight into the development of crucial parameters such as electrochemical potentials, corrosion currents and the electrical resistivity of the concrete. A less known but very beneficial field of application is the use of corrosion monitoring as an integral part of a repair measure based on principles such as the cathodic protection of steel in concrete (CP) or increasing the electrical resistivity of the concrete (IR). By implementing a corrosion monitoring system, it is possible to survey the time dependent effect of the repair measure on the corrosion process which may lead to a confirmation of successful repair measure or to a modification of the repair strategy.
As the principle of cathodic protection for steel in concrete is a recognized repair measure today, the number of applications increases steadily and thus increasing the relevance for corrosion monitoring. Nevertheless, no standards or guidelines concerning the corrosion monitoring are available in Germany today, making it difficult to implement corrosion monitoring in common practice.
With this in mind an international task group formed to develop the specification B12 “Corrosion Monitoring of Reinforced and Prestressed Concrete Structures” published by the German Society for Non-Destructive Testing, DGZfP, spring 2018.
This paper will present the new specification B12 by highlighting the basic measurement principles and illustrating the potentials of corrosion monitoring for new and existing concrete structures by means of case studies.
According to the results of the experiments carried out, the following points can be concluded:
1. Exposure tests showed that specimens with the addition of SiO2 particles and polyaniline particles exhibit better corrosion resistance than specimens with the addition of only polyaniline particles or binder only.
2. Open circuit potential measurements showed that in the beginning of the experiments, both coatings had an open circuit potential 100 mV higher than carbon steel. Within one day of immersion, the potential of carbon steel increased significantly, indicating the formation of oxide layer. After extended exposure the carbon steel potential sat between PS1 (which had higher potential) and PS2 (which had a lower potential) and all three were in the range –600 mV to –500 mV vs Ag/AgCl.
3. Both coatings PS-1 and PS-2 were degraded with increasing exposure time, shown by the decrease of absolute impedance value at low frequency range after 2, 4, and 6 days exposure.
4. Potentiodynamic test was performed after 3 hours and 6 days exposure, and it was shown that the coating in the initial stage exhibited more passive behavior than the specimens exposed for 6 days.
Susceptibility of 304 stainless steel to crevice corrosion in electrochemically active fluids
(2019)
The susceptibility of AISI 304 stainless steel to crevice corrosion on the effect of contact with electrochemically active fluids was investigated using exposure and stepwise potentiostatic polarisation. Crevice materials made up of 304 SS and Polyether ether ketone (PEEK) forming two kinds of crevices including 304 SS-to-PEEK and 304 SS-to-304 SS were tested.
Carbon Capture and Storage (CCS) is identified as an excellent technology to reach the target of CO2 reduction. However, the safety issue and cost-effectiveness hinder the future of CCS. For the reliability and safety issues of injection wells, the corrosion resistance of the materials used needs to be determined.
In this study, representative low-cost materials including carbon steel 1.8977 and low alloyed steel 1.7225 were investigated in simulated pore water at 333 K and under CO2 saturation condition to represent the worst-case scenario: CO2 diffusion and aquifer fluid penetration. These simulated pore waters were made from relevant cement powder to mimic the realistic casing-cement interface. Electrochemical studies were carried out using the pore water made of cement powder dissolved in water in comparison with those dissolved in synthetic aquifer fluid, to reveal the effect of cement as well as formation water on the steel performance. Two commercially available types of cement were investigated: Dyckerhoff Variodur® and Wollastonite. Variodur® is a cement containing high performance binder with ultra-fine blast furnace slag which can be used to produce high acid resistance concrete. On the other hand, Wollastonite is an emerging natural material mainly made of CaSiO3 which can be hardened by converting to CaCO3 during CO2 injection.
The results showed the pH-reducing effect of CO2 on the simulated pore water/aquifer (from more than 10 to less than 5) leading to the active corrosion process that happened on both 1.8977 and 1.7225. Electrochemical characterization showed negative free corrosion potential and polarisation curves without passive behaviors. The tested coupons suffered from pitting corrosion, which was confirmed by surface analysis. Interestingly, basing on the pit depth measurements from the tested coupons and the hardness of cement powder, it is suggested that Variodur® performed better than Wollastonite in both aspects. The electrochemical data was compared to that resulted from exposure tests to give a recommendation on material selection for bore-hole construction.
By exposure and electrochemical tests in the laboratory the Cu-effect on corrosion behavior of carbon steel, high-alloyed steels and Ti-alloy can be assessed.
Critical materials specific properties were determined by static exposure and electrochemical tests in an artificial geothermal water with high salinity and low pH, containing Cu. Conclusions were drawn using characteristic potential values.
It could be shown that significant Cu-deposition and -precipitation only occurred in combination with carbon steel. High-alloyed materials (S31603, S31653, S31700, S31703, S31803 and N08904) prevent the disturbing Cu-agglomeration. Therefore, they are suitable to be chosen for future design of the piping system, either in massive or in cladded form, if formation of crevices with non-metallic materials can be excluded.
From the interactions and pitting corrosion point of view, R50400 seems to be most favorable.
Ein neuer Ansatz bei elektrochemischen Korrosionsuntersuchungen kann durch den Einsatz von gelartigen Elektrolyten als Alternative zu wässrigen Prüfelektrolyten beschritten werden. Gelartige Elektrolyte ermöglichen minimalinvasive Untersuchungen an natürlich gebildeten Zinkdeckschichten. Dadurch können korrosionsrelevante Kennwerte ermittelt werden, die Aussagen zur Deckschichtbildung und zur Stabilität von atmosphärisch gebildeten Deckschichten erlauben. In diesem Beitrag wird anhand verschiedener Untersuchungen an Reinzink der Mehrwert von gelartigen Elektrolyten für die Korrosionsforschung und -prüfung verdeutlicht. Darüber hinaus werden neue Erkenntnisse zur Deckschichtbildung von Zink unter atmosphärischen Bedingungen vorgestellt.
Metallene Konstruktionswerkstoffe reagieren infolge ihres thermodynamisch instabilen Zustandes mehr oder weniger stark mit Stoffen aus der Umgebung. Eine große Rolle bei diesen Reaktionen spielt das Feuchtigkeitsangebot an der Metalloberfläche, welches nicht zwingend mit einem sichtbaren Wasserfilm einhergehen muss. An der Atmosphäre bilden sich an sauberen Metalloberflächen bei etwa 80 % relativer Luftfeuchte, bei versalzten Oberflächen auch schon ab etwa 25 % r. F., Feuchtfilme aus. Im Feuchtfilm laufen grundsätzlich die gleichen elektrochemischen Reaktionen ab, wie diese von wässrigen Medien bekannt sind. Dabei geht das Metall zunächst in Ionenform und in nachgelagerten Reaktionen in einen thermodynamisch stabilen Zustand in Form unterschiedlichster Oxid- und Hydroxidverbindungen über. Die so entstehenden Korrosionsprodukte können im Feuchtigkeitsfilm begrenzt löslich oder unlöslich sein und lagern sich auf den Oberflächen der Konstruktionswerkstoffe häufig als feste Korrosionsprodukte ab bzw. wachsen dort auf. Je nachdem wie die Korrosionsprodukte strukturell zum Untergrund passen, können sich dichte, sehr gut haftende Schichten ausbilden oder poröse, dicke Schichten ohne nennenswerte Haftung aufwachsen. Wachsen dichte, porenfreie Schichten mit guter Haftung auf, die im umgebenden Medium unlöslich sind, wird die weitere Auflösung des Metalls stark gehemmt. Man spricht dann von der Ausbildung schützender Deckschichten bzw. von Passivschichten auf welcher der Korrosionsschutz und damit die Dauerhaftigkeit vieler Konstruktionswerkstoffe beruhen. Kaesche bezeichnete die Passivität sehr treffend als „optimalen Grenzfall des Korrosionsschutzes durch Schichten von Korrosionsprodukten“. Aus technischer Sicht hält Kaesche eine Unterscheidung von Deckschichten bzw. Passivschichten für nicht zwingend erforderlich, da beide die Korrosionsgeschwindigkeit in gleichem Maß herabsetzen können. Die Übergänge zwischen den meist dickeren und dadurch sichtbaren Deckschichten und den meist dünnen, nicht sichtbaren Passivschichten sind fließend.
Investigation of the salinization in marine and offshore environment - test methods and challenges
(2019)
Salinization and contamination of metal surfaces by chloride-containing aerosols is of great importance with regard to corrosion phenomena in the maritime sector and in offshore applications. Especially Offshore Wind Turbines are exposed to extreme corrosive conditions due to high chloride concentrations in the atmosphere and the resulting high chloride deposition rates. It is of great importance to evaluate to what extent salinization of the surface influences the corrosion protection of coatings and pitting occurrence on stainless steels under atmospheric conditions to evaluate the durability of metallic building structures in offshore and marine environments. The evaluation of the scientific literature and regulatory guidelines has shown that there are still many open questions regarding the contamination of metal surfaces by chlorides. This contribution will discuss how salinization of metal surfaces is evaluated and monitored according to current standards and guidelines. Future challenges concerning test methods and the application of evaluated salinization values and deposition rates will be discussed.
Specific amounts of oxidizing and reductive impurities as well as some moisture were added to dense phase CO2 to replicate CO2 streams from sources in a CCS pipeline network. Due to the moisture content being only 50 ppmV no visible acid condensation took place. To simulate stress conditions at the inside pipeline surface due to fluid pressure (10 MPa) specimens were preloaded using a load frame. Experiments conducted at 278 K and at 313 K revealed the highest corrosion rate at lower temperature. Corrosive effect of impurities was strongest applying mixed atmosphere, containing oxidizing and reductive components, closely followed by CO2 streams with pure oxidizing character. By far, the lowest corrosion rate (10x lower) resulted from reductive atmosphere. In general, at constant temperature and pressure the CO2 stream composition strongly influences the morphology, thickness and composition of the corrosion products. Applying oxidizing or mixed impurities, iron hydroxides or oxides (e.g. goethite, hematite) occur as dominating corrosion products, capable to incorporate different amounts of sulfur. In contrast, using reductive atmosphere very thin corrosion layers with low crystallinity were developed, and phase identification by XRD was unfeasible. SEM/EDX analysis revealed the formation of Fe-O compounds, most likely attributed to the oxygen partial pressure in the system induced by CO2 (≥0.985 volume fraction) and volatile H2O. In addition to the surface covering corrosion layer, secondary phases had grown locally distributed on top of the layer. These compounds are characteristic for the applied atmosphere and vary in number, shape and chemical composition.