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Une transition mondiale vers des systèmes énergétiques plus durables, abordables et fiables a été initiée par l’accord de Paris et l’Agenda 2030 des Nations unies pour un développement durable. Il s’agit là d’un défi industriel majeur car les systèmes et infrastructures énergétiques résilients au changement climatique exigent de se positionner pour le long terme. Se pencher sur le comportement dans la durée des matériaux structurels - principalement des métaux et des alliages - s’impose alors comme une nécessité. Dans cette optique, « La corrosion : un défi pour une société durable »présente une série de cas montrant l’importance de la tenue à la corrosion et de la protection anticorrosion des métaux et des alliages pour le développement de systèmes durables, économiques et fiables de production d’énergie.
Galvanic corrosion protection by embedded zinc anodes is an accepted technique for the corrosion protection of reinforcing steel in concrete. Galvanic currents flow between the zinc anode and the steel reinforcement due to the potential difference that is in the range of a few hundred mV.
The ion distribution was studied on two steel reinforced concrete specimens admixed with 3 wt.% chloride/wt. cement and galvanically protected by a surface applied EZ-anode. On both specimens, a zinc anode was embedded and glued to the concrete surface by a geo-polymer-based chloride-free binder. At one specimen, the EZ-anode was operated for 2,5 years, the EZ-anode at the other specimen was not electrically connected to the reinforcement, this specimen serves as a reference. Both specimens have been stored under identical conditions. The ion distribution between the anode (EZ-ANODE) and cathode (steel reinforcement) was studied by laser-induced breakdown spectroscopy (LIBS) after 7 months, 12 months, and 2,5 years. Results of the LIBS studies on the specimen with activated EZ-anode after 7 months, 12 months, and 2,5 years and of the reference specimen after 2,5 years are reported. Results show that diffusion of ions contributes to the changes in the ion distribution but migration, especially of chlorides towards the EZ-anode is significant despite the weak electric field – several hundred millivolts - generated by the galvanic current. Results show that chloride ions accumulate near the zinc-anode as in water-insoluble zinc-hydroxy chlorides - Simonkollite.
To mitigate carbon dioxide emissions CO2 is compressed and sequestrated into deep geological layers (Carbon Capture and Storage CCS). The corrosion of injection pipe steels is induced when the metal is in contact with CO2 and at the same time the geological saline formation water. Stainless steels X35CrMo17 and X5CrNiCuNb16-4 with approximately 17% Cr show potential as injection pipes to engineer the Northern German Basin geological onshore CCS-site. Static laboratory experiments (T = 60 ◦C, p = 100 bar, 700–8000 h exposure time, aquifer water, CO2-flow rate of 9 L/h) were conducted to evaluate corrosion kinetics. The anomalous surface corrosion phenomena were found to be independent of heat treatment prior to exposure. The corrosion process is described as a function of the atmosphere and diffusion process of ionic species to explain the precipitation mechanism and better estimate the reliability of these particular steels in a downhole CCS environment.
Static immersion tests of potential injection pipe steels 42CrMo4, X20Cr13, X46Cr13, X35CrMo4, and X5CrNiCuNb16-4 at T = 60 °C and ambient pressure, as well as p = 100 bar were performed for 700–8000 h in a CO₂-saturated synthetic aquifer environment similar to CCS sites in the Northern German Basin (NGB). Corrosion rates at 100 bar are generally lower than at ambient pressure. The main corrosion products are FeCO₃ and FeOOH with surface and local corrosion phenomena directly related to the alloy composition and microstructure. The appropriate heat treatment enhances corrosion resistance. The lifetime reduction of X46Cr13, X5CrNiCuNb16-4, and duplex stainless steel X2CrNiMoN22-5-3 in a CCS environment is demonstrated in the in situ corrosion fatigue CF experiments (axial push-pull and rotation bending load, 60 °C, brine: Stuttgart Aquifer and NGB, flowing CO₂: 30 L/h, +/- applied potential). Insulating the test setup is necessary to gain reliable data. S-N plots, micrographic-, phase-, fractographic-, and surface analysis prove that the life expectancy of X2CrNiMoN22-5-3 in the axial cyclic load to failure is clearly related to the surface finish, applied stress amplitude, and stress mode. The horizontal grain attack within corrosion pit cavities, multiple fatigue cracks, and preferable deterioration of austenitic phase mainly cause fatigue failure. The CF life range increases significantly when a protective potential is applied.
The suitability of an Al2O3 coating for corrosion protection on X20Cr13 was evaluated in various artificial geothermal brines, focusing on the influence of different pH (4, 6 and 8) and their chemical compositions on the coating properties. All experiments were performed in the laboratory using autoclaves at 150 ◦C and 1 MPa in deaerated condition for 1 and 7 days. Results showed that the pH of geothermal waters is the most detrimental factor in the transformation of ɣ-Al2O3 and its protective abilities. Delaminations were found in the Coating exposed to geothermal brines with pH 4. FTIR spectra indicated a transformation of ɣ-Al2O3 to boehmite AlOOH after exposure to pH 4 and 6, and bayerite Al(OH)3 was formed after exposure to pH 8. Different Crystal structures of the hydrated Al2O3 also contribute to the stability of the coatings, observed by the SEM- EDX of the surface and cross-section of coatings. This study indicated that ɣ-Al2O3 sol-gel coating presents a promising aspect of corrosion protection in geothermal environment with a neutral pH.
Often 3D‐printing and additive manufacturing are mentioned as the 3rd industrial revolution. In this conjunction this book provides a brief overview on additively manufactured metal pieces.
This book fulfills its intension to serve as an educational guide, providing a holistic picture encompassing science, technology and applications for the real‐life use of Metal Additive Manufacturing.
In 2019 CRC Press published the "Steel‐Reinforced Concrete Structures" as a paperback. This book does not vary in terms of content from the hardback publication of 2008. But it is first reviewed here in corrosion news. The book provides eight of nine chapters in which the author discusses technical aspects of assessment and repair of steel‐reinforced concrete structures.
To sum up, this book is recommended for students and people involved with the assessment and repair of reinforced‐concrete structures, who want to get a quick introduction into the different aspects of the field. Readers also learn much about the economic interactions besides the topic. However, for experienced technicians and corrosion experts, this book may not be exact enough in both the electrochemical description of deterioration processes and the practical aspects of repair and control methods. Despite that, the discussions of the author are scientifically correct.
In coal-fired power plants using oxyfuel combustion process with carbon capture and sequestration, instead of air, a mixture of oxygen and recirculated flue gas is injected in the boiler. A series of steels were exposed to CO2-SO2-Ar-H2O gas mixtures at 600 °C for 1000 h to compare their high temperature corrosion behavior. During the corrosion process, carburization, decarburization and recrystallization were observed underneath the oxide scale depending on the gas mixture and alloy composition. The conditions that lead to carburization are not yet completely understood, but decarburization can be simulated using thermodynamic and kinetic models. In this work, the results of these simulations are compared with measured values for one of the alloys that displayed a decarburized region. Since the mobility of carbon in the scale is not known, two strategies were adopted: simulation of alloy-atmosphere contact; and estimation of the carbon flux to produce the observed decarburization. The second approach might give an insight on how permeable to carbon the scale is.
During capture and storage technology (CCS) as well as in geothermal energy production Steels need to withstand the corrosive environment such as: heat, pressure, salinity of the aquifer and CO2-partial pressure. 1.4542 shows unusual corrosion phenomena, but is still sufficiently resistant in corrosive environments. To better understand its behaviour differently heat treated coupons of 1.4542 and for comparison X20Cr13 and X46Cr13 were kept in the artificial brine of the Northern German Basin at T=60 °C. Ambient pressure as well as p=100 bar for 700 h - 8000 h in water saturated supercritical CO2 and CO2-saturated synthetic aquifer Environment was applied. Fatigue tests were performed via push-pull tests with a series of 30 specimens from 150 MPa to 500 MPa (sinusoidal dynamic test loads, R=-1; resonant frequency ~ 30 Hz). FeCO3 and FeOOH are corrosion products also after dynamic corrosion tests. Martensitic microstructure offers good corrosion resistance in geothermal environment. The S-N-curve showing no typical fatigue strength and very steep slopes of possible fatigue strength for finite life. Possible influencing artefacts, such as Al-inclusions could not be correlated to early rupture despite specimens containing inclusions at the fracture surface and cross section reached lower number of cycles. Applied potential proofed to enhance fatigue life tremendously.
Corrosion fatigue specimen with different surfaces (technical surfaces after machining and polished surfaces) of high alloyed martensitic stainless steel X46Cr13 (1.4043) and duplex stai nless steel X2CrNiMoN22 3 2 (1.4462) were compared at load amplitudes from 175 MPa to 325 MPa in the geothermal brine of the N orthern German Basin at 98 °C. Surface corrosion layers and pits reveal carbonate corrosion products on the surface such as FeCO 3 and FeOOH as the main precipitation phases with no dependence on the original surface roughness . At high stress amplitudes above 275 MPa technical surfaces (P50% at σa 300 MPa=5 × 10 5 ) resulted in more cycles to failure than polished (P50% at σa 300 MPa=1.5 × 10 5 ). The greater slope coefficient for technical surfaces k = 19.006 compared to polished surfaces k =8.78 demonstrate s earlier failure at given stress amplitude σa .
Machine learning based multi-sensor fusion for the nondestructive testing of corrosion in concrete
(2020)
Half-cell potential mapping (HP) is the most popular non-destructive testing method (NDT) for locating corrosion damage in concrete. It is generally accepted that HP is susceptible to environmental factors caused by salt-related deterioration, such as different moisture and chloride gradients. Additional NDT methods are able to identify distinctive areas but are not yet used to estimate more accurate test results. We present a Supervised Machine Learning (SML) based approach to data fusion of seven different signal features to obtain higher quality information. SMLs are methods that explore (or learn) relationships between different (sensor) data from predefined data labels. To obtain a representative, labelled data set we conducted a comprehensive experiment simulating the deterioration cycle of a chloride exposed device in the laboratory. Our data set consists of 18 measurement campaigns, each containing HP, Ground Penetrating- Radar, Microwave Moisture and Wenner resistivity data. We compare the performance of different ML approaches. Many outperform the best single method, HP. We describe the intrinsic challenges posed by a data-driven approach in NDT and show how future work can help overcome them.
Electrochemical deposition of polyaniline on carbon steel for corrosion study in geothermal solution
(2019)
Polyaniline has been widely developed for many applications, e.g. sensor, supercapacitor components, electrochromic devices, and anticorrosion pigments. Although the addition of polyaniline pigment in organic coatings has been an alternative for corrosion protection in industrial applications, the protection mechanism is still not fully understood. Herein in this study, as a part of the development of polyaniline/silicon dioxide coating for geothermal application, polyaniline has been deposited electrochemically on carbon steel surface in oxalic acid medium and tested in geothermal solution to understand the contribution of polyaniline to the corrosion protection of a polyaniline-based composite in the geothermal system. To observe the surface/interface reaction between the electrolyte and electrode surface during the electrochemical polymerization, electrochemical impedance spectroscopy (EIS) was applied after each cycle. For corrosion study in the geothermal application, an artificial geothermal solution was used with the composition of 1,500 mg/l Cl⁻, 20 mg/l SO₄²⁻, 15 mg/l HCO₃⁻, 200 mg/l Ca²⁺, 250 mg/l K⁺, and 600 mg/l Na⁺, and pH 4 to simulate a geothermal brine found in Sibayak, Indonesia. An electrochemical measurement was performed by monitoring the open circuit potential over seven days, with the interruption by EIS every 22 hours. The experiments were performed at room temperature and 150 °C (1 MPa) in an oxygen-free environment. Impedance spectra showed a reduction of the total impedance value of approximately 10 times for specimens measured at 150 °C compared to the specimens measured at room temperature, suggesting a less stable layer at high temperature.
The composites combining aluminum and silica nanoparticles with the addition of tetramethylammonium hydroxide (Al-SiO2(T)) and butanol (Al-SiO2(B)) as mixing media have been successfully fabricated. Corrosion behavior of Al-SiO2 composites before and after exposure in 1M NaCl solution was examined using potentiodynamic polarization (Tafel curve analysis). The study was also equipped with scanning electron microscopy (SEM), energy dispersive X-ray (EDX), and X-ray diffraction (XRD) investigations. Before exposure, Al-SiO2(T) exhibited the best corrosion resistance. Performance improvement was indicated by Al-SiO2(B) up to 10 times better than Al-SiO2(T) after exposure. The increased SiO2 content did not significantly enhance the corrosion resistance of the composites. The Al-SiO2 composites with 5% SiO2 content showed very high corrosion resistance (as the optimum composition). Furthermore, pitting corrosion was observed in the Al-SiO2 composites, indicated by the formation of corrosion products at grain boundaries. The product was affected by the presence of SiO2 in the Al matrix and the NaCl environment at 90 °C (approach to synthetic geothermal media: Na+, Cl, H+, OH-). Our study revealed the presence of γ-Al2O3, γ-Al(OH)3, and Al(OH)2Cl as the dominant corrosion products.
Carbon Capture and Storage (CCS) is well acknowledged to mitigate climate change. Therefore, pipe Steels suitable for CCS technology require resistance against the corrosive environment of a potential CCS-site, e.g. heat, pressure, salinity of the aquifer, CO2-partial pressure. Samples of different mild and high alloyed stainless injection-pipe Steels partially heat treated: 42CrMo4, X20Cr13, X46Cr13, X35CrMo4 as well as X5CrNiCuNb16-4 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in a CO2-saturated synthetic aquifer environment similar to possible geological on-shore CCS-sites in the northern German Basin. Main corrosion products analysed on pits are FeCO3 and FeOOH. The carbon content does not show significant influence on the pitting behaviour. Generally, higher chromium Content results in better corrosion resistance. Although X35CrMo17-1 and X5CrNiCuNb16-4 show low surface corrosion rates, their resistance against local corrosion in CCS environment is not significantly better compared to the much less costly Steels X20Cr13 and X46Cr13.
The development of alkali‐activated materials (AAMs) as an alternative to Portland cement (PC) has seen significant progress in the past decades. However, there still remains significant uncertainty regarding their long term performance when used in steel‐reinforced structures. The durability of AAMs in such applications depends strongly on the corrosion behaviour of the embedded steel reinforcement, and the experimental data in the literature are limited and in some cases inconsistent. This letter elucidates the role of the chemistry of AAMs on the mechanisms governing passivation and chloride‐induced corrosion of the steel reinforcement, to bring a better understanding of the durability of AAM structures exposed to chloride. The corrosion of the steel reinforcement in AAMs differs significantly from observations in PC; the onset of pitting (or the chloride ‘threshold’ value) depends strongly on the alkalinity, and the redox environment, of these binders. Classifications or standards used to assess the severity of steel corrosion in PC appear not to be directly applicable to AAMs due to important differences in pore solution chemistry and phase assemblage.
Potential of martensitic stainless steel X5CrNiCuNb 16-4 as pipe steel in corrosive CCS environment
(2017)
Pipe steels suitable for carbon capture and storage technology (CCS) require resistance against the corrosive environment of a potential CCS-site (heat, pressure, salinity of the aquifer, CO2-partial pressure). X5CrNiCuNb16-4 has been proven to be sufficient resistant in corrosive environments, but shows rather unusual corrosion behaviour in CCS environment. Therefore differently heat treated coupons of 1.4542 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in an a) water saturated supercritical CO2 and b) CO2-saturated synthetic aquifer environment similar to on-shore CCS-sites in the Northern German Basin. Additionally fatigue tests were performed via push-pull tests with a series of 30 specimens was tested at stress amplitudes between 150 MPa and 500 MPa (sinusoidal dynamic test loads, R=-1; resonant frequency ~ 30 Hz). Best corrosion resistance in the liquid phase is achieved via normalizing prior to exposure and hardening+tempering at 670 °C leads to lowest corrosion rates in the supercritical phase. With no regard to atmosphere discontinuously ellipsoidal surface corrosion regions appear after exposure of 4000 h and more. The endurance limit of X5CrNiCuNb16-4 measured in air is reduced by more than 50% when exposed to CCS environment (maximum number of cycles (10 x 106) at a stress amplitude of 150 MPa) The scatter range TN = 1:34 is disproportionately large contributing to an overall unusual corrosion behaviour.
Similar to the success story of digital photography a major upheaval has been observed in digital industrial radiology. This paper is split into 3 parts:
Part 1: Film Replacement and Backscatter Imaging: Computed radiography with phosphor imaging plates substitutes film applications. Digital Detector Arrays enable an extraordinary increase of contrast sensitivity in comparison to film radiography. The increased sensitivity of digital detectors enables the efficient usage for dimensional measurements and functionality tests substituting manual maintenance. The digital measurement of wall thickness and corrosion status is state of the art in petrochemical industry. Photon counting and energy discriminating detectors are applied up to 300 Kv provide increased thickness dynamic and material discrimination by synchronously acquisition of images of the high and low energy part of the spectrum. X-ray back scatter techniques have been applied in safety and security relevant applications with single sided access of source and detector. First inspections of CFRP in aerospace industry were successfully conducted with newly designed back scatter cameras. Numeric modeling is used to design X-Ray optics and inspection scenarios as well as conducting RT training.
Part 2: Computed tomography (CT)
Part 3: Micro Radiography and Micro CT.
Manganese alloyed stainless steels represent a cost-effective alternative to conventional CrNi- stainless steels due to strong fl uctuations of the market prices for nickel seen during the last years. In CrMnNi steels, nickel is partially replaced by lower-cost manganese and small amounts of nitrogen for stabilization of the austenitic phase. This also brings benefi ts regarding the mechanical properties, as it results in an increased material strength. Laser beam welding of such materials was investigated for direct comparison with Standard CrNi steels. Main emphasis was laid on fi nding adequate process parameters to achieve a stable welding process and obtain a good weld quality. Two different laser sources, a 4.4 kW Nd:YAG and a 5 kW CO2 laser, were used to weld 1.5 mm stainless steel sheets in continuous wave mode. A high-Mn austenitic (1.4376) and a lean duplex (1.4162) steel, as well as the standard austenitic (1.4301) and duplex (1.4362) grades were selected as test materials. Both butt and lap joint confi gurations were studied. Experiments were carried out systematically, varying the welding speed, laser power and focal point position in order to determine adequate process windows. The infl uence of the shielding gas type and fl ow rate on the process stability and the weld quality were investigated. The effects of weld edge preparation on the weld appearance and quality levels attained were also examined. The obtained welded joints were subjected to radiographic tests for detection of internal imperfections. Also a metallurgical characterization of the samples regarding the resulting phase composition or balance and hardness depending on the welding process parameters was conducted. Furthermore, tensile and potentiodynamic tests were performed to evaluate the mechanical and corrosion properties, respectively. The results provide an insight into the advantages and limitations of the laser beam welding process for joining high-manganese alloyed stainless steels. Conditions for the production of defect-free and corrosion-resistant welds having good mechanical properties could be determined.
In order to provide basic information on corrosion resistance to the designers and users of geothermal plants different metallic materials including duplex and austenitic stainless steels as well as a nickel alloy have been evaluated in artificial geothermal fluids simulating the conditions in some locations with geothermal potential in Germany as well as two sites in Indonesia. By electrochemical and long-term exposure tests at 100 °C and 150 °C the suitability of low alloyed steel UNS G41300, stainless steels UNS S31603 UNS S31803, UNS S32760, super austenitic steel UNS N08031 and nickel based alloy UNS N06059 was investigated in these geothermal fluids, using critical potentials and corrosion rates. In high-saline environments the crevice corrosion turned out to be the determining mechanism. The nickel based alloy shows excellent corrosion resistance against pitting corrosion. Excluding its high cost, it is very good to be used in the construction of geothermal facilities having highly saline brines. Stainless and duplex steels exhibit a limited corrosion resistance concerning pitting and crevice corrosion. Therefore they are not suitable for highly saline brines. The super austenite UNS N08031 showed a temperature depending behavior. In non-saline environments the low-alloyed steel UNS G41300 (beside of the higher alloyed materials) could be employed as a constructional material for the geothermal power plant, as long as a sufficient wall thickness of the material is considered.
LIBS is on the step from a laboratory application to on-site analysis. A validated mobile LIBS-system for on-site application on building materials is under development at BAM in cooperation with industrial partners (system developers and companies), who will use this technique for investigation on building structures like bridges and parking decks. The system is designed to measure the content of harmful species like chlorine, sulfur or alkalis, to give the engineer a tool for the estimation of the condition of concrete structures and for quality assurance during concrete repair work on-site. In these work results of on-site measurements on a chloride contaminated bridge are shown. Further work will focus on providing guidelines to establish LIBS as a standard procedure for chemical investigations of building materials.
When storage of spent nuclear fuel or high level waste is carried out in dual purpose casks (DPC), the effects of aging on safety relevant DPC functions and properties have to be managed in a way that a safe transport after the storage period of several decades is capable and can be justified and certified permanently throughout that period. The effects of aging mechanisms (e.g. radiation, different corrosion mechanisms, stress relaxation, creep, structural changes and degradation) on the transport package design safety assessment features have to be evaluated. Consideration of these issues in the DPC transport safety case will be addressed. Special attention is given to all cask components that cannot be directly inspected or changed without opening the cask cavity, like the inner parts of the closure system and the cask internals, like baskets or spent fuel assemblies. The design criteria of that transport safety case have to consider the operational impacts during storage. Aging is not the subject of technical aspects only but also of intellectual aspects, like changing standards, scientific/technical knowledge development and personal as well as institutional alterations. Those aspects are to be considered in the management system of license holders and in appropriate design approval update processes. The paper addresses issues that are subject of an actual International Atomic Energy Agency TECDOC draft 'Preparation of a safety case for a dual purpose cask containing spent nuclear fuel'.
The development of anti-corrosive pigments for the most diverse coating Systems is extremely time consuming and expensive, owing to the necessary climatic testing, such as testing under salt spray exposure. To accelerate work on a new zinc-free pigment with improved protection, modern, electrochemical investigation methods have been used successfully and verified using traditional tests.
Development of anti-corrosive pigments for diverse coating systems is both time-consuming and costly, due to the necessary climatic testing, such as testing under salt spray exposure. To accelerate work on a new zinc-free pígment with improved protection, modern, electrochemical investigation methods have been used successfully and verified using traditional tests.
Bei der Qualitätsbewertung von Schneidwaren aus nichtrostenden martensitischen Chrom-Stählen stellt die Überprüfung der Korrosionsbeständigkeit ein wichtiges Kriterium dar. Allgemein üblich sind Wechseltauchversuche mit relativ hohem zeitlichem und auswertungsbedingtem Aufwand, die noch dazu zerstörend sind und teilweise fragwürdige Ergebnisse liefern. In den letzten Jahren wurden neue Ansatze der Prüfung geschaffen, die eine nahezu zerstörungsfreie Kurzzeit-Korrosionsprüfung erlauben. Es wird gezeigt, dass mit dem elektrochemischen Rauschen sehr empfindlich Einflüsse des Härtens und der Oberflächenbehandlung auf die Korrosionsbeständigkeit nachgewiesen werden können, wodurch eine schnelle und objektive Qualitätsbewertung innerhalb des Fertigungsprozesses und der Endkontrolle von Produkten möglich ist. Das für die Prüfmethodik ausgenutzte Phänomen des elektrochemischen Rauschens zielt darauf ab, den Beginn der Korrosion empfindlich und schnell zu detektieren, ohne die Prüfbedingungen maßlos zu verschärfen und Produkte damit zu zerstören. Neben der Funktionalität der Prüfung stehen aber auch die Anwenderfreundlichkeit und somit die Akzeptanz bei den Herstellern im Vordergrund. Aus diesem Grund wurde zusätzlich ein Indikatortest (KorroPad) als praxistaugliche Alternative zum elektrochemischen Rauschen angewendet. Die Ergebnisse zeigen eine gute Übereinstimmung beider Methoden und ermöglichen eine effektive betriebliche Qualitätsüberwachung von Schneidwaren.
Alumosols in combination with well dispersed corundum were successfully used to form up to 2.5 ìm thick coatings on the Ni-base alloy SC16. These coatings withstood heat treatments at 700 °C in a water vapour containing atmosphere. The heat treatment caused formation of delta-alumina in the coating and diffusion of chromium and titanium into the coating.