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- Stainless steel (7)
- Pitting corrosion (6)
- Electrochemical noise (5)
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- Betonstahl (3)
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- KorroPad (3)
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Although zinc and zinc coatings have been widely used for corrosion protection for decades new zinc coatings are constantly being developed. Characterizing the corrosion protectiveness of these new coatings, however, should not be underestimated. While exposure tests are time intensive, cyclic tests can only be used for a very limited field of application. Thus, electrochemical measurements provide both an efficient and an effective alternative. Conventional aqueous bulk electrolytes influence the surface layers of a tested zinc coating and are therefore not reliable. Gel electrolytes, however, have evolved over the last few years, are minimally invasive and provide reliable results.
This work describes experiments with gel electrolytes made of agar. Unlike previous work, it proposes a composition of gel electrolyte for minimally invasive description of the protective power of naturally formed oxide layers on zinc and zinc coatings. Therefore, as a first part, the gel electrolyte made of agar is verified as a method for zinc and zinc-coated samples. Afterwards, this paper introduces the corrosion product layer resistance RL as a promising parameter to evaluate the protective power of zinc coatings. Results are verified with EIS and FTIR measurements. An example on a representative zinc coating demonstrates the practical application.
Agar gel pads have been used for electrochemical measurements for some time. For zinc in particular, a standard method for measuring the stability of the corrosion product layer is being established. The main interpretation factor is the corrosion product layer resistance RL, as it is easy to determine and interpret. A high corrosion product layer resistance indicates a high level of protection. However, it is not yet known how low the corrosion product layer resistance is for freshly produced zinc samples. As zinc is highly active, it reacts immediately with the environment to form a corrosion product layer, which affects the corrosion product layer resistance. The addition of zinc acetate to the agar gel pads prevents the formation of a surface layer and destroys existing ones.
This makes it possible to measure an almost corrosion product-free zinc surface. This is important in defining the range of corrosion product layer resistance for a protective surface.
Electrochemical noise (EN) enables corrosion research and monitoring in real time and with high sensitivity. In the case of submicroscopic nucleation events of pitting corrosion it has been observed that the cathodic process plays a decisive role in the mechanism as well as in the origin of EN signals, which depend not only on the metallic dissolution reaction but also on the electron-consuming process. EN signals arising from the nucleation process of localized corrosion on stainless steels can only be recorded due to the inhibition effect on the cathodic process achieved by the spontaneous formation of the passive layer. In consequence, passive layer stability becomes a significant factor in influencing EN signals. The way in which the passive layer stability affects the acquisition and analysis of EN signals arising from pitting corrosion on stainless steels is discussed in detail.
Unwanted corrosive phenomena on stainless steel surfaces like rouging had been observed for years occurring at certain service conditions. Rouging consists in the formation of a colored surface film containing mainly iron on metallic surfaces in contact with high-purity waters. In spite of numerous hypotheses and experimental examinations a clear explanation about the origin of rouging on stainless steels is currently still lacking. Because rouging occurs even at well passivated stainless steel surfaces the origin of this corrosive phenomenon should be related to the weakness of the stability of the passive film. In the present paper electrochemical noise measurements regarding the stability of the passive layer of alloy 904L (1.4539, X1NiCrMoCu25-20-5) in high-purity water at 70 °C depending on the cathodic process are presented. In addition, the importance of the cathodic reaction on the passivation and stability of the passive layer is discussed.
Electrochemical noise measurements on anodically polarised type 304 stainless steel surfaces in contact with buffer solutions of neutral pH were performed to study the effect of chloride ions in the nucleation of pitting corrosion. Passive layer stability and susceptibility to pitting corrosion after pickling and passivation at different environmental conditions were also investigated by means of electrochemical current noise measurements under cathodic and anodic polarisation. According to the obtained experimental results pits nucleate independently on the presence of chloride ions. It has been also shown that protectiveness of stainless steel surfaces after pickling strongly depends on the relative humidity of the environment in which the surface is subsequently passivated.
Samples of the austenitic stainless steel grade X5CrNi18‐10 (1.4301, AISI 304) were ground industrially with various grinding parameters to study their influence on corrosion resistance. The ability of the mechanically ground surfaces to form a stable passive layer was evaluated by KorroPad test and a modified electrochemical potentiodynamic reactivation test based on a single loop (EPR‐SL). Furthermore, the surfaces were characterized by surface analytical methods. The main influence was determined regarding abrasive belt type. Surfaces mechanically ground with granulate abrasive belts constantly had a lower corrosion resistance than surfaces ground with single‐coated grain. The granulate abrasive belts generated more sensitized surface areas and left formations of welded sample material on the mechanically ground surfaces. A post‐treatment with a nonwoven abrasive proved to be an effective finishing process by which the surface defects and sensitized material got removed and the surfaces regained the expected corrosion resistance.
Risiko der Wasserstoffentwicklung an martensitischen Schraubankern unter baupraktischen Bedingungen
(2020)
Die vorliegende Untersuchung beschäftigt sich mit der Fragestellung, ob unter praxisrelevanten Bedingungen die Entstehung von Wasserstoff an vollmartensitischen Schraubankern möglich ist. Im Gegensatz zu austenitischen Werkstoffen besteht bei martensitischen Werkstoffen bei Gegenwart von Wasserstoff stets die Möglichkeit einer wasserstoffinduzierten Versprödung des Materials. Hierfür wurde ein in der Praxis häufig anzutreffendes Szenario gewählt, das ein galvanisches Element, bestehend aus nichtrostenden Schraubankern (in diesem Fall martensitischen) und einer verzinkten Ankerplatte an einem Betonkörper, umfasst. Zum Nachweis einer Wasserstoffentwicklung werden der Elementstrom zwischen den Bauteilen sowie das Korrosionspotential erfasst. Die Ergebnisse der Versuche zeigen, dass über eine zeitlich begrenzte Dauer eine starke kathodische Polarisation der martensitischen Schraubanker durch die korrosive Auflösung des Zinks erfolgt. Als Folge kommt es zur Wasserzersetzung im Phasengrenzbereich der Schraubanker und zur Entstehung von atomarem Wasserstoff. Das berechnete Gasvolumen des entstandenen Wasserstoffs an den Stahlankern wurde bestimmt und lag im Mittel bei 11,14 ± 1,94 ml. Eine Diffusion des an der Stahloberfläche adsorbierten Wasserstoffs in den martensitischen Werkstoff ist somit theoretisch möglich und impliziert eine mögliche Gefährdung durch wasserstoffinduzierte Rissbildung und spontanes Versagen unter Belastung.
About the long-term protection behaviour of corrosion protection materials (filling materials) for prestressed systems under critical environmental conditions is only little known. The corrosion protection effect is usually based on theoretical considerations and is proven by short-term tests. The selection of the different products is mainly made according to economical or workability criteria. In a research project the barrier effect of different commercial corrosion protection materials (waxes as well as oil-based greases) against water, their tendency for undercutting as well as their additional corrosion protection effect were investigated. The exposure tests were carried out with non-stressed as well as stressed prestressing steel specimens which were subjected to critical conditions (condensed water, artificial soil solution, direct soil contact). Parallel to these long-term exposure tests the applicability of different electrochemical techniques and their significance with respect to testing the corrosion protection ability and water absorption was evaluated. Within the project a suitable method for simple testing the performance of corrosion protection materials under real conditions was developed. By means of a small compact cell submicroscopical reactions of the used sensors could be measured. The high sensitivity of this measuring technique enables the detection of degradation processes at thin protection layers.
In order to clarify under which practical conditions real risks for hydrogen-induced stress corrosion cracking of prestressing steels exist laboratory investigations in aqueous solutions and concrete as well as tests with stressed prestressing steels were carried out. While different distances between steel and zinc (cathode and anode) showed only a negligible influence on the polarisation of the steel a significant dependence on the area ratio steel/zinc was observed. A critical area ratio of 10:1 can be defined above which polarisation of the steel to hydrogen evolution potentials is unlikely. The results obtained in the laboratory concerning the critical area ratio were confirmed by on-site investigations in a precasting plant. Exposure tests with hydrogen loading did not lead to fractures during the testing time for approved prestressing steels. The characteristic mechanical values determined immediately after the hydrogen loading tests did not show significant changes. Thus, an indirect contact between prestressing steels and galvanised elements can be estimated as uncritical. But a direct contact has to be excluded by compliance with DIN 1045-1, i.e minimal distance of 2 cm between prestressing steel and galvanised elements.
Chloride-induced damage of reinforcing steel is especially for parking garages and bridges often very severe as large amounts of chlorides act on horizontal surfaces which could lead to fast ingress of these detrimental ions up to the level of the reinforcement and subsequently to high rates of corrosion.
In order to avoid the disadvantages of conventional rehabilitation (unreliable prognosis with patch repair or high costs and regular maintenance with cathodic protection using impressed current) a new combined protection system was developed where the principle of drying out the concrete (by means of a surface protection system) is combined with a temporary cathodic protection (by means of a sprayed zinc layer) during the transitional period of the drying out process.
This new system was tested both in the laboratory and on-site at a pilot application. Based on the results obtained the possibilities and limitations of the new system are discussed in this paper.
Eine der wesentlichsten Veränderungen der im Oktober 2015 erschienenen Neufassung der DIN EN 1993-1-4 findet sich im Anhang A „Werkstoffauswahl und Dauerhaftigkeit“. Im Gegensatz zur Vorgängerversion ist dieser Anhang jetzt normativ. Mit Hilfe eines Punktesystems, das die wichtigsten Einwirkungsparameter der relevanten Expositionsbedingungen berücksichtigt, wird eine Korrosionsbeständigkeitsklasse ermittelt, mit deren Hilfe man eine geeignete Legierung auswählen kann. Dieses Verfahren bietet eine zuverlässige Methode für Planer auch ohne spezielle Kenntnisse auf dem Gebiet der Korrosion bzw. der nichtrostenden Stähle. Die Arbeit geht auch auf Unterschiede sowie Gemeinsamkeiten mit der bisher in Deutschland gültigen allgemeinen bauaufsichtlichen Zulassung Z-30.3.6 ein.
Anhand der hier vorgestellten Untersuchungsergebnisse kann
eine umfassende Einschätzung des Korrosionszustands einer Gabionenkonstruktion aus Drähten mit Zink-Aluminium-Überzug nach 20 Jahren Einsatzzeit in Abhängigkeit von unterschiedlichen Expositionsbedingungen vorgenommen werden. Die festgestellten Massenverluste der Zink-Aluminium-Überzüge waren an den Untersuchungspositionen, insbesondere hinsichtlich der verschiedenen Expositionsbedingungen der Probenentnahmestellen, unterschiedlich ausgeprägt. Gabionendrähte, die im direkten Bodenkontakt standen, wiesen dabei die geringsten Restauflagen auf. Atmosphärisch beanspruchte sowie durch Vlies vor direktem Bodenkontakt geschützte Gabionendrähte zeigten dagegen etwas größere Restauflagen. Über den Drahtumfang wurden bei allen untersuchten Drahtproben stark variierende Schichtdicken festgestellt, was offensichtlich herstellungsbedingte Ursachen hat. Die Untersuchungen an der Gabionenkonstruktion haben gezeigt, dass die Annahme einer mittleren linearen Abtragsrate des metallischen Überzugs von 1 mm/a unter den hier untersuchten Bedingungen ein realistischer Wert ist. An Positionen mit direktem Bodenkontakt kann dieser Wert aber deutlich größer ausfallen, sobald sich die Aggressivität des Bodens erhöht. Eine Rotrostbildung war an den Drahtproben nicht feststellbar.
The presented investigations have proved the principal suitability of the KorroPad method to assess the passive layer stability of stainless steels. The electrochemical mode of action could be described in detail and limitations of the applicability have been demonstrated. The influence of different surface finishes has been investigated and verified by known methods for describing corrosion resistances. As a result, the increased corrosion susceptibility of two ground surfaces has been detected, but also the corrosion resistance of further surface finishes could be confirmed.
The present work describes the combination of electrochemical investigations by using a gel‐type electrolyte with Fourier‐transformed infrared spectroscopy to investigate partially extremely thin corrosion product films on titanium‐zinc. The gel pad method enables the determination of corrosion relevant parameters such as the potential and the linear polarization resistance without altering the corrosion product layers, which are extremely prone to re‐dissolution when freshly formed. Complementary infrared spectroscopy enables the determination of main compounds of even very thin surface layers of few tenth of nanometers with a certain lateral resolution. It was found that zinc forms mostly zinc carboxy‐hydroxides such as hydrozincite, under various exposure conditions. The protective properties of these hydrozincite layers depend on the structure of the corrosion product film rather than on its thickness. In mid‐term exposure tests, shallow corrosion pits were found even in the absence of corrosive agents such as chloride.
Surface treatments usually are used to modify the appearance and properties of stainless steel surfaces. Simultaneously, the corrosion resistance of the stainless steel surface being related intrinsically to the spontaneous formation of a passive layer also will be affected. In this respect, the influence of different surface treatments on the corrosion resistance of Type 304 (UNS S30400) stainless steel to pitting corrosion has been evaluated by means of potentiostatic electrochemical noise measurements and surface characterization. Typical industrial treatments including mechanical grinding, glass blasting, and pickling were taken into account. Additionally, special consideration was put on the effect of aging conditions of the passive layer after surface treatments, in particular on the relative humidity. Benefits and limitations of the different applied surface treatments concerning protectiveness of the stainless steel surface were determined and discussed.
Die Potentialfeldmessung ist ein Standardverfahren zur Zustandserfassung von Stahlbetonbauwerken. Sie dient der zerstörungsfreien Detektion von aktiv korrodierenden Bereichen. Die Aussagegenauigkeit der Potentialfeldmessung ist von großer wirtschaftlicher Bedeutung, da deren Messergebnisse eine wichtige Entscheidungsgrundlage für die Erarbeitung von Instandsetzungsmaßnahmen bilden. Zur Ermittlung der Aussagegenauigkeit der Potentialfeldmessung wird ein numerisches Verfahren vorgestellt. Die wichtigsten Einflussgrößen auf die Potentialfeldmessung wie Anodengröße, Elektrolytwiderstand und Messraster wurden im Hinblick auf die Aussagegenauigkeit ausgewertet.
Zur vergleichenden Einschätzung der Lochkorrosionsbeständigkeit von verschiedenen, mehrlagigen MAGp-auftraggeschweißten Nickelbasis-Schweißgütern auf einem Superduplexstahl wurden kritische Lochkorrosionstemperaturen (critical pitting temperature, CPT) nach ASTM G 48 C ermittelt. Es zeigte sich eine unerwartet niedrige Beständigkeit der Auftragschweißungen, als dessen Ursache ein ungünstiger Oberflächenzustand angenommen wurde. Da die CPT-Bestimmung nach ASTM keine Aussage über den Korrosionsverlauf gestattet und Untersuchungen über einen weiten Temperaturbereich damit sehr aufwendig sind, wurde eine neue Prüfmethode angewandt. Diese ermittelt die CPT mit Hilfe des elektrochemischen Stromrauschens zwischen zwei gleichartigen Proben in der nach ASTM G 48 C geforderten Prüflösung bei kontinuierlicher Temperaturerhöhung. Dadurch war es möglich, den Einfluss des Oberflächenzustandes auf das Lochkorrosionsverhalten der untersuchten Proben schnell nachzuweisen und geeignete Maßnahmen zu ergreifen. Der beim MAGp-Schweißen entstehende oxidische Oberflächenbelag beeinflusst die Lochkorrosionsbeständigkeit negativ. Nach der mechanischen Beseitigung der Beläge durch Strahlen oder Schleifen weisen die Proben eine wesentlich höhere Lochkorrosionsbeständigkeit auf, und es konnte die Abhängigkeit von der Anzahl der Schweißlagen ermittelt werden.
Translated Abstract
Pitting corrosion behaviour of built-up welds - Effects of welding layers and tarnish -
The pitting corrosion resistance of nickel based deposition welds on a superduplex steel made by active-gas metal pulsed-arc welding was studied. Therefore the determination of the CPT (Critical Pitting Temperature) should be carried out corresponding to ASTM G 48 C. However an unexpectedly low resistance of the built-up welds also at multilayer order was noticed.
After visual assessment of the examined specimens a significant effect of the surface condition was assumed. Because the CPT determination according to ASTM does not allow any statement about the corrosion process, this method was not suitable to characterize the corrosion system. For this reason a new method was applied to clarify the causes of the low corrosion resistance. This method determines the CPT with the help of the electrochemical current noise under the same conditions demanded in ASTM G 48 C. The temperature is increased continuously and the characteristic parameters of the system are recorded and evaluated objectively within short time. So it was possible to see the influence of the surface condition on the pitting corrosion behaviour of the examined specimens. The required parameters to the post-processing of the deposition welds were determined. The comparison of the results show that the surface tarnish formed after the shielded arc welding process influences the pitting corrosion resistance negatively. After its elimination the CPT could be determined in dependence of the welding layers.
Auf dem Gebiet des mechanischen Fügens ist eine rege Entwicklung zu verzeichnen. Der Einsatz neuer Materialien, neuer Nietformen, neuer Schutzschichten, veränderter Fertigungstechnologien, die Notwendigkeit zur Mischbauweise, veränderte mediale Belastungen, geforderte Langzeitgarantien usw. lassen vielfältige alte und neue Fragen hinsichtlich der Korrosionsbeständigkeit auftreten. Herkömmliche Korrosionsprüfverfahren geben oft nur unzureichende Antworten auf diese Fragen. Mit dem Einsatz des elektrochemischen Rauschens ist es möglich, in kurzer Zeit aussagekräftige Ergebnisse über Material- und Bauteileigenschaften zu erhalten, da eine Metalloberfläche ständig Signale über ihren Zustand aussendet, auch wenn man nicht misst. Neben der Möglichkeit, die Korrosionsneigung zu bestimmen, lassen sich über die Rauschmessungen auch bestimmte Verarbeitungsfehler und Oberflächendefekte nachweisen. Die Anwendung dieser Methode bietet somit Möglichkeiten zur Prozessoptimierung und Qualitätssicherung mechanisch gefügter Bauteile, oder auch zur Einschätzung bestehender Fügeverbindungen.
Translated Abstract
Application of noise measurement for the early detection of corrosion property of mechanical joined metal sheets
In the area of mechanical joining an active development is to be registered. The use of new materials, new rivet forms, new protective layers, changed production technologies, use of mixed materials, changed medial loads, demanded long-term guarantees etc. let arise various old and new questions regarding the corrosion resistance. Conventional corrosion testing methods often give only insufficient answers to these questions. With the use of the electrochemical noise it is possible to receive meaningful results over material and construction characteristics within a short time since a metal surface constantly sends signals over its condition, even if one does not measure. Apart from the possibility of determining the probability of corrosion also certain processing errors and surface defects can be proven with noise measurements. Thus the application of this method offers possibilities for the process optimization and quality assurance of mechanically joined construction units, or also for the estimation of existing joining connections.
In der industriellen Praxis ist die Sprühnebelprüfung eine häufig eingesetzte Prüfmethode zum Nachweis der Produktqualität von Halbzeugen und Zulieferteilen hinsichtlich ihrer Korrosionsbeständigkeit. Aus diesem Grund gehören die Klima- und Sprühnebelprüfungen zu den am weitesten verbreiteten Korrosionsprüfverfahren. Jedoch kann man über den zeitlichen Verlauf der Korrosion, ob linear, exponentiell, logarithmisch o.ä. keine Aussage treffen. Weiterhin sind die Prüfbedingungen bei den Sprühnebelprüfungen verschärft, um eine Verkürzung der Messzeit zu erreichen. Damit verändert man unter Umständen die Korrosionsmechanismen. Die Sprühnebelprüfung kann jedoch auch ohne Verwendung von zu scharfen, praxisfremden Prüfmedien deutlich an Erkennbarkeit gewinnen, indem man elektrochemische in-situ Messungen (Rauschmessungen) anwendet. Im Gegensatz zu herkömmlichen elektrochemischen Messungen, bei denen die untersuchten Proben von einem bulk-Elektrolyten umgeben sind, basieren die Messungen unter Sprühnebelbedingungen auf der Bildung eines Elektrolytfilms an den Probenoberflächen, sowie an den Innenwänden der Prüfkammer und der Anbauten (z. B. Probenhalter). Die Messeffekte weichen nicht grundlegend von konventionellen Messungen ab, die nutzbaren Signale sind jedoch von den Eigenschaften des Elektrolytfilms (Ausbreitung auf der Oberfläche, Leitfähigkeit, Dicke) abhängig. Die erfolgreiche Anwendung von Rauschmessungen unter Sprühnebelbedingungen wird für einige Beispiele der Korrosionsprüfung gezeigt.
Translated Abstract
Instrumentation of salt-spray test procedures
Salt-spray test procedures are frequently used in industrial practice as a test method for proof of product quality with semi-finished products and received parts with regard to their corrosion resistance. For this reason, salt-spray testing is one of the most well-established corrosion test procedure. However, no statement can be made about the way in which corrosion develops over time (linear, exponential or logarithmic). Furthermore, the test conditions for salt-spray tests are intensified in order to shorten the measuring times, which can lead to a change in the corrosion mechanism. Nevertheless, also without intensifying test conditions salt-spray testing can be brought to a qualitatively higher level and the clarity of the results can be improved by means of in-situ electrochemical noise measurements. In contrast to established electrochemical tests in which the specimens are surrounded by a common bulk electrolyte, electrochemical measurements in the spray chamber are based on the development of an electrolyte film on the surface of the specimen, but also on the inside walls of the testing chamber and on all fittings present (e. g. specimen holder). The measured effect thus has the same basis as in conventional electrochemical measurements. The exploitable signal is limited by the shortest connection route between the specimens, as well as by the thickness and the conducting ability of the electrolyte film. The successful application of noise measurements under salt-spray conditions is shown on various examples for corrosion testing.
Für Korrosionsprüfungen stehen eine ganze Reihe bewährter und standardisierter Verfahren zur Verfügung, die eine weite Verbreitung gefunden haben. Dazu gehören die Sprühnebelverfahren, Klimaprüfverfahren, Auslagerungsversuche in spezifisch wirkenden Prüfmedien und die elektrochemische Polarisationsmesstechnik. Dennoch bleiben eine ganze Reihe von Fragen und Wünschen offen. Insbesondere die Anfangsprozesse der Korrosion lassen sich häufig nur unzureichend untersuchen. Auch über den zeitlichen Verlauf der Korrosion geben die eingesetzten Verfahren keine ausreichenden Informationen. Weiterhin führt der Wunsch nach möglichst praxisnahen Prüfbedingungen bei vertretbarem Aufwand und die Suche nach Möglichkeiten zur Verkürzung von Prüfzeiten zur ständigen Weiterentwicklung der Prüf- und Untersuchungsmethoden.
In der Korrosionsforschung steht mit der Rauschdiagnostik bei der Untersuchung von Korrosionsprozessen ein einfaches, empfindliches und nahezu zerstörungsfreies Messverfahren zur Beurteilung der Korrosionsneigung metallischer Werkstoffe zur Verfügung. Mit dem heutigen Kenntnisstand über das elektrochemische Rauschen bei Korrosionsprozessen können die Einsatzmöglichkeiten sowohl auf die Lösung von Messaufgaben im Labor, als auch auf spezielle Probleme bei der Korrosionsüberwachung in der Praxis erweitert werden. Des Weiteren findet diese Methode auf Grund ihrer spezifischen Vorteile auch immer mehr Anwendung zur Unterstützung bzw. Verbesserung herkömmlicher Korrosionsprüfungen. Der Zugewinn wichtiger Erkenntnisse, die Verkürzung von Prüfzeiten sowie die damit verbundene Schonung von Ressourcen (Arbeitskraft, Energieaufwand, chemische Hilfsmittel etc.) sind einige der Vorteile, die eine moderne Korrosionsprüfung heute kennzeichnen.
Translated Abstract
Electrochemical noise measurements - Innovation in corrosion testing
There are a lot of approved and standardized methods available for corrosion testing which have found wide application. Salt-spray testing, electrochemical polarization techniques and exposure tests in specific test media belong to these. Nevertheless, some questions remain unanswered and requirements unsatisfied. In particular, both the start of corrosion and the way it proceeds with time can often be examined only to an insufficient extent. Furthermore, the requirements of practical test conditions, acceptable effort and expenditure and shorter test durations lead to continuous development of these test methods.
Within corrosion research, the analysis of electrochemical noise offers a simple, sensitive and virtually non-destructive measuring technique for assessment of the corrosion susceptibility of metallic materials and for the investigation of corrosion processes. The present status of knowledge concerning noise diagnostics in corrosion processes permits the application of this method not only to experimental tasks in the laboratory, but also to special problems in the context of practical corrosion monitoring. Furthermore, specific advantages of the technique enable its use to an increasing extent in supporting or improving conventional corrosion testing. The advantages here include obtaining additional information and shortening testing times (together with associated savings in resources such as manpower, energy, chemical reagents, etc.), thus resulting in state-of-the art corrosion testing.
In indoor swimming pools stainless steels are used not only due to structural and economic reasons but also due to aesthetic considerations. And therefore not only safety relevant load bearing components have to fulfil their tasks but also the visual appearance should be free of any staining. In a lot of cases basic requirements (e.g. design criteria, material selection and maintenance) being essential parts of technical regulations were not taken into account. Typical case studies with explanation of the cause of the corrosion problems and possibilities to prevent them are shown in the present paper.
Electrochemical noise measurements on unalloyed steel in chloride-containing alkaline environment
(2007)
The investigations discussed in this paper aim to clarify whether electrochemical noise measurements (ENM) are capable for application in concrete and mortar, particularly with regard to pitting initiation in such environment. For these purposes, the results of several different test series are compared and discussed. Based on investigations on passivity and pitting corrosion in alkaline solutions with different chloride contents further results in cement paste, mortar and concrete are evaluated.
Aufgrund der in den letzten Jahren stark angestiegenen Rohstoffpreise sind die im Bauwesen häufig eingesetzten nichtrostenden Standardaustenite in vielen Fällen nicht mehr wettbewerbsfähig. Eine deutlich kostengünstigere Alternative stellt der Duplex-Stahl 1.4362 dar, der bisher aber noch nicht bauaufsichtlich zugelassen ist. Mit Hilfe von Auslagerungsversuchen sowie elektrochemischen Untersuchungen sollte das Korrosionsverhalten dieses Werkstoffs unter neutralen bis leicht sauren, chloridhaltigen Umgebungsbedingungen, wie sie in vielen Bereichen des Bauwesens vorkommen, geklärt werden. Insgesamt belegen die Ergebnisse, dass der kostengünstigere Werkstoff 1.4362 für baupraktische Anwendungen eine Alternative für Anwendungen darstellen kann, in denen bisher die Werkstoffe 1.4404 oder 1.4571 eingesetzt wurden.
Steel in concrete is protected by the alkaline pore water environment and the resulting formation of a protective passive layer against corrosion. Adverse environmental conditions due to carbonation or chloride ingress can destroy the passive layer on the steel surface. Corrosion processes starting in those areas lead to uniform corrosion or local corrosion like pitting corrosion. In comparison to uniform corrosion pitting corrosion is a form of increased local corrosion and thus leads to a progressive reduction in cross-section of the reinforcing steel. The corrosion products are first absorbed by the pores of the concrete matrix, without causing visible external changes at the concrete surface.
Electrochemical potential mapping according to guideline B3 of DGZfP (German Society for Nondestructive Testing) is a recognized technique for the localization of corroding reinforcing steels. In reinforced concrete structures the measured potentials are not necessarily directly linked to the corrosion likelihood of the reinforcing steel. The measured values may be significantly affected, different from, e.g., stress measurement, by different influences on the potential formation at the phase boundary metal/concrete itself as well as the acquisition procedure. Due to the complexity of influencing factors there is a risk that the results are misinterpreted. Therefore, in a training concept firstly the theoretical basics of the test method should be imparted. Then, frequently occurring practical situations of various influencing factors will be made accessible to the participants by a model object specially designed for this purpose. The aim is to impart profound knowledge concerning the characteristics of potential mapping for detecting corrosion of reinforcing steel in order to apply this technique in practice as reliable and economical test method.
The reduction of the chromate contents in cements affects the electrochemical reactions of galvanized reinforcing steels in fresh concrete. By means of electrochemical measurements and bar pull-out tests the effect of chromates on the formation of protective coatings at the zinc and the bond behaviour have been investigated using chromate-containing and chromate-reduced cements. The results have shown that the bond zone was affected as a result of chromate reduction for cement types CEM I and CEM II. The disturbance to the bond zone should be considered as long-term in relation to the pore structure which is formed. The effects on the bond are largely compensated for as the concrete ages. The results of the related bond strength with displacement paths of 0.1 and 0.5?mm, respectively, are still within the range of expected figures for non-galvanized reinforcing steel despite the structural disturbance. Under practical aspects it is not necessary that the existing structural disturbance with respect to bond strength is taken into consideration.
Korrosions- und Verbundverhalten verzinkter Betonstähle in Betonen mit chromatreduzierten Zementen
(2011)
Durch die Absenkung des Chromatgehalts der Zemente verändern sich die elektrochemischen Reaktionen von verzinkten Betonstählen in der Frischbetonphase. Mit Hilfe von elektrochemischen Messungen sowie Stabauszugsversuchen wurde an chromathaltigen und chromatreduzierten Zementen die Auswirkung des Chromats auf die Deckschichtbildung am Zink und auf das Verbundverhalten untersucht.
Mit den Ergebnissen konnte eine Beeinträchtigung der Verbundzone als Folge der Chromatreduzierung für die Zementarten CEM I und CEM II nachgewiesen werden. Die Störung der Verbundzone ist in Bezug auf die sich ausbildende Porenstruktur als dauerhaft anzusehen. Die Auswirkungen auf das Verbundverhalten werden mit zunehmendem Betonalter weitgehend kompensiert. Die Ergebnisse der bezogenen Verbundspannung bei Verschiebewegen von 0,1 mm und 0,5 mm liegen trotz der Gefügestörung noch im Bereich der Erwartungswerte für den unverzinkten Betonstahl. Unter baupraktischen Gesichtspunkten muss die auftretende Gefügestörung hinsichtlich der Verbundspannung daher keine Berücksichtigung finden.
Der maßgebliche Korrosionsschutz von nicht rostendem Stahl in Beton basiert, anders als bei unlegiertem Betonstahl, auf der Ausbildung einer Chromoxidschicht. Die Chromoxidschicht ist in alkalischem und in carbonatisiertem Beton beständig, sodass nicht rostende Stähle in einem passiven Zustand vorliegen.
Die Initiierung von Lochkorrosionserscheinungen ist dagegen auch an nicht rostenden Stählen in Beton möglich. Der korrosionsauslösende Chloridgehalt ist neben dem Gehalt an Legierungselementen (insbesondere dem Chromgehalt) und der Oberflächenbeschaffenheit auch vom Konzentrationsverhältnis von OH“ zu CI“ im Elektrolyten abhängig. Daher ist prinzipiell zu erwarten, dass in karbonatisierten Betonen geringere Chloridgehalte Korrosion initiieren können als in Betonen mit höheren pH-Werten. Dies gilt in besonderem Maße für nicht rostende Betonstähle mit geringen Chromgehalten, wie z. B. Produkte aus dem Werkstoff 1.4003 (X2CrNi12) mit seiner im Vergleich zu den Standardausteniten geringen Beständigkeit. Um den kritischen korrosionsauslösenden Chloridgehalt am Beispiel eines am Markt verfügbaren ferritischen Chromstahls zu bestimmen, wurden an der Bundesanstalt für Materialforschung und -prüfung (BAM) umfangreiche Untersuchungen zu beschleunigten Korrosionsversuchen in alkalischen und karbonatisierten Mörteln durchgeführt. Mittels Laser-induced Breakdown Spectroscopy (LIBS) konnten die korrosionsauslösenden Chloridgehalte im Phasengrenzbereich Betonstahl-Mörtel ermittelt werden.
Investigation of chloride-induced pitting corrosion of steel in concrete with innovative methods
(2016)
The combination of electrochemical and 3D computed tomography (CT) investigations offers the possibility of verifying electrochemical measurements non-destructively. Determining the steel surfaces damaged by pitting corrosion allows developing specimens having damage pattern corresponding to practice. Corrosion phenomena like decoupled pitting corrosion cannot be verified by electrochemical measurements only, but with the combination of those two kinds of investigations it is possible. Another advantage is the minimization of the number of samples. The classical experimental procedure requires the destruction of samples after each damage step.This can be avoided by the use of 3D computed tomography. As long as the corrosion phenomena are completely within the examination zone shown by the 3D computed tomography, the electrochemical measurements can be calculated on an area basis to get the specific corrosion rate or polarization resistance.
Die Erzeugung geschliffener Oberflächen bei hochlegierten Chrom-Nickel-Stählen aus dekorativen Gründen z. B. beim Einsatz im Bereich Innenarchitektur kann sich u. U. problematisch hinsichtlich der Korrosionsbeständigkeit auswirken. Bei den Untersuchungen zum Einfluss der Verfahrensparameter beim industriellen Schleifen zur Erzeugung eines bestimmten optischen Erscheinungsbildes stellte sich heraus, dass die Rauheit allein kein Maß für die zu erwartende Korrosionsbeständigkeit darstellt. Die Variation verschiedener Schleifparameter, aber auch die Art des Schleifmittels können einen erheblichen Einfluss auf die Korrosionsbeständigkeit ausüben. Neben den Ergebnissen verschiedener Auslagerungsversuche werden elektrochemische Untersuchungen an den geschliffenen Oberflächen vorgestellt. Dabei konnte mittels elektrochemischer Rauschmessungen die unterschiedliche Korrosionsneigung der Oberflächen nachgewiesen werden.
Translated Abstract
The influence of grinding treatment of stainless steels on the corrosion behaviour
Mechanical grinding of stainless steels is often used for decoration purposes, for instance in the interior decoration. However, this treatment can cause problems regarding the corrosion resistance. During investigations of the influences of processing parameters of industrial grinding it was shown, that roughness only is not the expected crucial parameter for the corrosion resistance. The variation of different grinding parameters and also the type of abrasives have a substantial influence. Beside the long term tests electrochemical investigation at the ground surfaces are presented. The different corrosion susceptibility of the surfaces could be proven by means of electrochemical noise measurements.
Nine different stainless steel alloys were exposed for 5 years under marine environment and their corrosion behaviour was compared and assessed. The investigation of four different surface finishes for all alloys tested further enabled to consider industry-specific features of the surface finish for the material comparison. The results of the exposure tests yield conclusions regarding the influence of alloy composition, surface finish and exposure duration under marine environment. The three duplex stainless steels revealed excellent corrosion resistance even in case of crevices during the 5 years of exposure under the given exposure conditions. Also the molybdenum-alloyed ferritic steel 1.4521 showed good corrosion resistance comparable to the classical austenitic materials 1.4301 and 1.4404.
An einem Tankbehälter aus dem Werkstoff X2CrNiMo17-12-2, der zur Zwischenlagerung von Salzlake für die Käseherstellung dient, wurden trotz langjähriger positiver Erfahrungen an vergleichbaren Anlagen bereits kurze Zeit nach der Inbetriebnahme Lochkorrosionserscheinungen festgestellt. Durch entsprechende elektrochemische Laboruntersuchungen konnte gezeigt werden, dass die vorgefundene Lochkorrosion durch den Einsatz eines Oxidationsmittels zu Desinfektionszwecken verursacht wurde.
Translated Abstract
Corrosion damage at storage tanks for salt brine
A tank made of stainless steel type X2CrNiMo17-12-2 for intermediate storage of salt brine for cheese production revealed significant pitting corrosion effects shortly after commissioning although comparable units have shown positive long-term behaviour. By means of electrochemical laboratory tests it could be demonstrated that the observed pitting corrosion was caused by the use of an oxidizing agent for desinfection purposes.
Durch systematische Labor- und Auslagerungsuntersuchungen ist es möglich, sieben unterschiedliche nichtrostende Stahllegierungen hinsichtlich verschiedenster Anwendungen untereinander und auch in Bezug auf zwei austenitische Standardwerkstoffe (1.4301, 1.4404) zu vergleichen. Die parallele Untersuchung von fünf verschiedenen Oberflächenausführungen der jeweiligen Werkstoffe ermöglicht zudem, branchenspezifische Besonderheiten der Oberflächenausführung beim Werkstoffvergleich zu berücksichtigen. Der Einfluss der Oberflächenausführung wird überwiegend bei den Ergebnissen der Auslagerungsversuche in kritischen Atmosphären sichtbar, weniger bei den elektrochemischen Untersuchungen.
Die drei Vertreter aus dem Bereich der Duplexstähle zeigten unter den meisten Untersuchungsbedingungen eine hervorragende Korrosionsbeständigkeit. Insbesondere für Anwendungen im Bauwesen können die Lean-Duplexstähle deutliche Vorteile bieten. Der Manganaustenit 1.4376 sowie der Ferrit 1.4509 sind nur eingeschränkt als Alternativen geeignet, da die Werkstoffe bei einigen Versuchen signifikante Schwächen zeigten.---------------------------------------------------------------------------
The systematic laboratory and field exposure tests allow to compare seven different stainless steels among each other and also regarding two standard austenitic materials (1.4301, 1.4401) with respect to various applications. Parallel investigations with five different surface finishes of the respective materials enable to consider also industry-specific features of the surface finish. The influence of the surface finish can mainly be seen in the results of the exposure tests in critical atmospheres and less in the electrochemical investigations.
The three duplex stainless steels showed under most of the test conditions excellent corrosion resistance. Especially for applications in civil engineering the lean duplex steels offer clear advantages. The manganese alloyed 1.4376 and the ferritic steel 1.4509 are only limited suitable as alternatives as these materials showed significant weaknesses in some of the tests.
Systematic laboratory and field exposure tests allow to compare nine different stainless steels (three ferritic, three austenitic, and three duplex grades) for civil engineering applications. The influence of surface finish was also taken into account by choosing five different industry-specific features. The three duplex stainless steels revealed excellent corrosion resistance under most of the test conditions. Especially for applications in civil engineering the lean duplex steels offer distinct advantages. The manganese-alloyed 1.4376 and the ferritic steel 1.4509 cannot be recommended as alternative materials as they did not perform satisfactorily.
Um zu klären, unter welchen Umständen eine potentielle Gefährdung von Spannstählen beim Kontakt mit verzinkten Bauteilen gegeben ist, wurden Laborversuche in alkalischen Lösungen und Beton sowie Zeitstandversuche an Spannbetonprobekörpern durchgeführt. Abstandsvariationen im Nahbereich haben nur einen geringen Einfluss auf die Polarisation des Stahls. Ein praxisrelevanter, unkritischer Abstand für den indirekten Kontakt, z. B. über die schlaffe Bewehrung, kann nicht definiert werden. Hinsichtlich des Flächenverhältnisses Stahl : Zink wurde ein signifikanter Einfluss festgestellt. Flächenverhältnisse über 10 : 1 führen nicht zu einer Polarisation in den Bereich der Wasserstoffentwicklung. Die Ergebnisse wurden durch Untersuchungen an realen Spannbetonfertigteilen verifiziert.
Zeitstandversuche unter Wasserstoffbeladung führten an zugelassenen Spannstählen nicht zu Brüchen während der Versuchszeit. Die anschließend ermittelten mechanischen Kennwerte zeigten keine signifikanten Änderungen. Ein indirekter Kontakt von Spannstählen zu verzinkten Einbauteilen ist deshalb als unkritisch zu bewerten. Der direkte Kontakt ist durch Einhaltung des in der DIN 1045-1 geforderten Mindestabstands von 2 cm sicher auszuschließen.
In addition to constructional requirements in civil engineering stainless steels often have to fulfil high visual demands. Unexpected impairments of the visual appearance of stainless steels under low corrosive conditions are a widespread problem today. Frequently it is supposed that this is caused by changes in the alloy composition, worse environmental conditions or improper handling. Within a research project the systematic investigation of several cases of damaged stainless steel bars has shown that the reasons are based on well-known material defects like chemical inhomogeneities (e.g. precipitations or local carburization) or geometrical defects (e.g. undercuts, rolling defects or shell formation). Thus, the failures could be clearly identified as production failures of the respective semi-finished products.
Neben konstruktiven Anforderungen werden an nichtrostende Stähle im Bauwesen häufig hohe optische Ansprüche gestellt. Unerwartete Beeinträchtigungen des optischen Erscheinungsbildes nichtrostender Stähle unter wenig korrosiven Bedingungen sind in der Zwischenzeit ein weit verbreitetes Problemfeld und Gegenstand zahlreicher Streitfälle. Vielfach wird die Vermutung geäußert, dass eine veränderte Legierungszusammensetzung, veränderte Umweltbedingungen oder auch die unsachgemäße Verarbeitung die Ursache für diese Erscheinungen sind. Durch eine systematische Untersuchung zahlreicher Schadensfälle an Stabmaterial in den vergangenen zwei Jahren im Rahmen eines Forschungsvorhabens konnte gezeigt werden, dass die Ursachen in bekannten Werkstofffehlern zu finden sind. Hierzu gehören chemische Inhomogenitäten, wie zum Beispiel Ausscheidungen und örtliche Aufkohlung, sowie geometrische Fehler, wie zum Beispiel Hinterschnitte, Walzfehler und Schalenbildung. Die Fehler konnten damit eindeutig als Herstellungsfehler der jeweiligen Halbzeuge identifiziert werden.
Pitting corrosion is one of the most common mechanisms of surface damage on stainless steels. Electrochemical methods have been preferentially applied for the evaluation of the pitting corrosion resistance of stainless steels in the laboratory. Nevertheless, some of them are not reliable enough and in general the application of electrochemical methods in the field becomes difficult because of required deep understanding of corrosive phenomena and measurement technology. Therefore, new approaches for the evaluation of the pitting corrosion susceptibility of stainless steel surfaces in the laboratory as well as in the field are necessary. In the present paper two novel strategies including electrochemical noise measurements under anodic polarization for laboratory testing, and an indicator test to assess the susceptibility of stainless steel surfaces to pitting corrosion in the field are introduced. Experimental results concerning the influence of surface treatments on the pitting corrosion resistance on stainless steels have confirmed that final surface condition has a significant effect on their future pitting corrosion susceptibility. In addition, the pitting corrosion resistance of stainless steel surfaces was observed being specifically dependent on the achieved surface topography and in some cases independent on the roughness parameters of the surface.
Corrosion of steel reinforcement in concrete exposed to chloride containing environments is a serious problem in civil engineering practice. Electrochemical methods, e.g., potential mapping, provide information whether the steel reinforcement is still passive or depassivation has been initiated. By applying such techniques no information on the type of corrosion, its extent and distribution of corrosion products is available. Particular the corrosion progress is a significant problem. Especially in the case of macrocell corrosion in reinforced concrete structures, the development at the anode cannot be separated into corrosion damage resulting from macrocell corrosion or self-corrosion. Until now also in laboratory tests it is impossible to collect such information without destroying specimens after electrochemical testing was performed. To overcome this problem it was tried to study the steel surface within the mortar specimens by X-ray tomography (CT). Within the scope of these investigations it could be shown, that X-ray tomography is suitable to make corrosion pits and their development visible which are embedded in a mortar with a cover thickness of about 35 mm. In this publication the time-dependent corrosion damage of reinforced steel is documented by X-ray tomography.
The paper presents the damage model of German Research Unit 537 which was used as a working hypothesis for the development of a user-friendly design model. Excerpts from the laboratory experiments and numerical calculations processed in project A of the research unit are presented here. The excerpts include the quantification of self-corrosion, geometrical effects in the macrocell corrosion, development of corroding steel surface and pit depth as well as the quantification of the resistivity of the concrete and the corrosion of steel in cracked concrete.
The corrosion resistance of aluminium surfaces is closely linked to the surfacecstate after a grinding process. For years, iron‐containing abrasive materials were suspected to lead to increased corrosion susceptibility after processing of aluminium surfaces. To prove a possible correlation between the iron content of an abrasive and the corrosion behaviour of aluminium components, scientific investigations and experimentally practical corrosion tests are necessary.
For the current investigation, specimens of a technical Al‐Si alloy from the same batch were used. The test specimens were mechanically ground with various resin‐bonded model abrasives containing different iron contents. The performed corrosion tests did not reveal a negative influence of the different iron‐containing abrasives on the corrosion behaviour of the Al–Si alloy.
However, the most sensitive measuring method (electrochemical noise)
showed differences in the surface activity depending on the type of abrasive.
The salinization and contamination of metal surfaces by chloride-containing aerosols is of great importance with regard to corrosion phenomena of damaged coated metal surfaces and stainless steels in the maritime sector and in offshore applications. Detailed questions have to be answered to clarify whether and to what extent salinization of the surface has an influence on the adhesion and durability of coatings in repairing applications and on pitting occurrence on stainless steels under atmospheric conditions. The questions arise which degree of salinization is reached after which period of time and how a defined and reproducible salinization can be simulated in the laboratory for further systematic investigations. The article is dedicated to these questions. Results of a field trial on the Island of Heligoland are presented and a simple procedure for a defined loading of metal surfaces with chlorides at a laboratory scale using a design of experiments (DoE) approach is introduced.
The corrosivity of atmospheres in Europe has changed significantly in recent decades. For the Federal Republic of Germany, no current values for the corrosion rate based on 1‐year atmospheric exposure of standard specimens can be found in the scientific literature after 2000. This paper presents results from a field exposure study in the Berlin metropolitan area and Helgoland in 2016. Based on standard specimens, values for the corrosion rate and the corresponding atmospheric corrosivity category are determined for open exposure and indirect weathering in a ventilated enclosure as sheltering after 1 year of exposure. The results prove that determined corrosivity categories are material‐specific. Sheltered exposure is a typical atmospheric situation for many building components. It allows statements on the effect of the concentration of airborne substances on the corrosivity beyond the normative requirements.
Pitting corrosion is one of the most common mechanisms of local passivity breakdown on stainless steels. Electrochemical methods have preferentially been applied for the evaluation of pitting corrosion resistance of stainless steels in laboratory. Nevertheless, some of them are not reliable enough and in general the application of electrochemical methods in the field becomes difficult because of a required deep understanding of corrosion phenomena and measurement technology. A new approach for the evaluation of the pitting corrosion susceptibility of stainless Steel surfaces in the laboratory as well as in the field is frequently demanded by representatives of the metalworking industry. Therefore, the KorroPad-test was invented and patented as part of a research project at the BAM Federal Institute for Materials Research and Testing in Germany.