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Industries transporting CO2 gas-saturated fluids have infrastructures made of carbon steel. This is a good material with great mechanical properties but prone to corrosion and potential failure. Corrosion in sweet environments involves the formation of FeCO3 as a corrosion film, which is recognized to play a protective role under certain conditions. This work on the dissolution of corrosion films in sweet environments, under acidic and undersaturated conditions, demonstrates that the effects on the integrity of steel are far more significant than the damage observed on the surface of the corrosion film. Our results prove that dissolution of FeCO3 involved the presence of an amorphous phase, the intermediate formation of FeCl2 or FeCl+, and the presence of a phase with short distance atom–atom correlations. The amorphous phase was identified as a mixture of retained γ-Fe and Fe3C. Partially broken α-Fe and Fe3C structures were identified to prove the damage on the material, confirming the interface zone without evident damage on the corrosion film. Dissolution affected both the α-Fe and FeCO3, with the lattice [102̅] from the FeCO3 crystalline structure being the fastest to dissolve. The damage of steel at the molecular scale was evident at the macroscale with pit depths of up to 250 μm. The impact on the integrity of steel can be, therefore, more drastic than frequently reported in industrial operations of CO2 transport industries that use cleaning procedures (e.g., acid treatment, pigging) as part of their operational activities.
Civilization and modern societies would not be possible without manmade materials. Considering their production volumes, their supporting role in nearly all industrial processes, and the impact of their sourcing and production on the environment, metals and alloys are and will be of prominent importance for the clean energy transition. The focus of materials discovery must move to more specialized, application-tailored green alloys that outperform the legacy materials not only in performance but also in sustainability and resource efficiency. This white paper summarizes a joint Canadian-German initiative aimed at developing a materials acceleration platform (MAP) focusing on the discovery of new alloy families that will address this challenge. We call our initiative the “Build to Last Materials Acceleration Platform” (B2L-MAP) and present in this perspective our concept of a three-tiered self-driving laboratory that is composed of a simulation-aided pre-selection module (B2L-select), an artificial intelligence (AI)-driven experimental lead generator (B2L-explore), and an upscaling module for durability assessment (B2L-assess). The resulting tool will be used to identify and subsequently demonstrate novel corrosion-resistant alloys at scale for three key applications of critical importance to an offshore, wind-driven hydrogen plant (reusable electrical contacts, offshore infrastructure, and oxygen evolution reaction catalysts).
This paper considers an indirect measurement approach to reconstruct a defect in a two-dimensional waveguide model for a non-destructive ultrasonic inspection via derivative-based optimization. The propagation of the mechanical waves is simulated by the scaled boundary finite element method that builds on a semi-analytical approach. The simulated data are then fitted to given data associated with the reflected waves from a defect which is to be reconstructed. For this purpose, we apply an iteratively regularized Gauss-Newton method in combination with algorithmic differentiation to provide the required derivative information accurately and efficiently. We present numerical results for three kinds of defects, namely, a crack, delamination, and corrosion. The objective function and the properties of the reconstruction method are investigated. The examples show that the parameterization of the defect can be reconstructed efficiently as well as robustly in the presence of noise.
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.
Molten salt containing systems gain in importance for sustainable energy use and production. For research and development, interactions of molten salts with potential container materials are of major interest. This article introduces preparation procedures to display an intact metal and salt microstructure and their interface using light optical microscopy and scanning electron microscopy. The exemplary material combination is the ternary salt mixture NaCl-KCl-MgCl2 and the low alloyed steel 1.4901 (T92) with a maximum service temperature of 550 °C. These are potential elements/materials for use in latent heat thermal energy storages.
This work presents the determination of the corrosion characteristics of CrCoNi (medium entropy alloy) and CrMnFeCoNi (high entropy alloy) in 0.1 M NaCl and 0.1 M H2SO4. The morphology and chemical composition of the oxide layers formed on CrCoNi and CrMnFeCoNi were comparatively analyzed by scanning Kelvin probe microscopy (SKPFM) and scanning electron microscopy (SEM) and supported with chemical analysis by means of inductively coupled plasma mass spectrometry (ICP-MS) and X-Ray photoelectron spectroscopy (XPS). The analysis of the 3p core level peaks showed that the oxide layer (native and after anodic passivation) on CrCoNi consisted mainly of Cr oxides, while the oxide layer on CrMnFeCoNi was primarily composed of a mixture of Cr and Fe oxides. In addition, XPS was utilized to assess the oxide layer thicknesses. These results were compared to the thicknesses obtained by means of electrochemical impedance spectroscopy (EIS), with both approaches yielding values up to about 4 nm depending on the electrolyte and the alloy. Cyclic polarization measurements indicated superior corrosion resistance of CrCoNi in both aqueous environments compared to CrMnFeCoNi, as well as to AISI 304 stainless steel.
A global transition towards more sustainable, affordable and reliable energy systems is being stimulated by the Paris Agreement and the United Nation's 2030 Agenda for Sustainable Development. This poses a challenge for the corrosion industry, as building climate‐resilient energy systems and infrastructures brings with it a long‐term direction, so as a result the long‐term behaviour of structural materials (mainly metals and alloys) becomes a major prospect. With this in mind “Corrosion Challenges Towards a Sustainable Society” presents a series of cases showing the importance of corrosion protection of metals and alloys in the development of energy production to further understand the science of corrosion, and bring the need for research and the consequences of corrosion into public and political focus. This includes emphasis on the limitation of greenhouse gas emissions, on the lifetime of infrastructures, implants, cultural heritage artefacts, and a variety of other topics.
Biofilms are ubiquitous in nature and in the man-made environment. Given their harmful effects on human health, an in-depth understanding of biofilms and the monitoring of their formation and growth are important. Particularly relevant for many metabolic processes and survival strategies of biofilms is their extracellular pH. However, most conventional techniques are not suited for minimally invasive pH measurements of living biofilms. Here, a fluorescent nanosensor is presented for ratiometric measurements of pH in biofilms in the range of pH 4.5–9.5 using confocal laser scanning microscopy. The nanosensor consists of biocompatible polystyrene nanoparticles loaded with pH-inert dye Nile Red and is surface functionalized with a pH-responsive fluorescein dye. Its performance was validated by fluorometrically monitoring the time-dependent changes in pH in E. coli biofilms after glucose inoculation at 37 °C and 4 °C. This revealed a temperature-dependent decrease in pH over a 4-h period caused by the acidifying glucose metabolism of E. coli. These studies demonstrate the applicability of this nanosensor to characterize the chemical microenvironment in biofilms with fluorescence methods.
Cellulose ethers, like methyl cellulose (MC) or hydroxypropyl cellulose (HPC), are widely used in conservation. They also occur as additives and rheology modifiers in various products like dispersions or gels. Do such products release harmful volatile organic compounds (VOC) during their accelerated aging? A mass testing series utilizing the Oddy test of 60 commercial cellulose ethers ranks the products in safe for permanent use (P, no corrosion), only for temporary use (T, slight corrosion), and unsuitable at all (F, heavy corrosion). Results show that 55% of the products passed the test whereas 33% are for temporary use as slight corrosion occurred on at least one metal coupon and only 11% failed the Oddy test. Raman measurements of the corrosion products identified oxides like massicot, litharge, cuprite, and tenorite among carbonates (hydrocerussite, plumbonacrite), and acetates like basic lead acetate, lead acetate trihydrate as well as lead formate as main phases. For example, commercial, industrial Klucel® G (HPC) scored a T rating through slight corrosion on the lead coupon. Basic lead acetate among other phases indicates the presence of acetic acid. Additional measurements of the sample with thermal desorption GC–MS utilizing the BEMMA scheme confirm the high acetic acid outgassing and reveal the presence of a small amount of formaldehyde.
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.
Early material damage in equimolar CrMnFeCoNi in mixed oxidizing/sulfiding hot gas atmosphere
(2022)
The challenges to use more varied fuels at medium and high temperatures above 500 °C need to be addressed by tuning the materials toward a better resistance against increased corrosion. As a first step the corrosion processes need to be better understood, especially in the case of the unavoidable and highly corrosive sulfur-based gases. Herein, oxidation/sulfidation of an equimolar CrMnFeCoNi high-entropy alloy is studied at an early stage after hot gas exposure at 600 °C for 6 h in 0.5% SO2 and 99.5% Ar. The oxidation process is studied by means of X-ray diffraction, scanning and transmission electron microscopy, and supported by thermodynamic calculations. It is found that the sulfur does not enter the bulk material but interacts mainly with the fast-diffusing manganese at grain boundary triple junctions at the alloy surface. Submicrometer scaled Cr–S–O-rich phases close to the grain boundaries complete the sulfur-based phase formation. The grains are covered in different Fe-, Mn-, and Cr-based spinels and other oxides.
Novel agar-based test electrolytes are used to perform electrochemical corrosion investigations on ZnFe and ZnNi binary as well as ZnFeMo ternary zinc coatings. The objectives of the electrochemical investigations include the characterization of the corrosion behavior, the description of the protective effect of the coatings as well as the investigation of the layer formation and degradation under artificial aging. ZnFe and ZnFeMo coatings are applied with varying iron content as well as an additional passivation layer, respectively, to study the effect on corrosion resistance. The results show that the protective effect of the coatings is not negatively influenced by different iron contents or the addition of molybdenum. Additional passivation of the ZnFe-containing coatings by means of a passivating agent leads to a significant improvement in the protective effect. Artificial aging leads to slight degradation of the additional passivation layer whereas coatings without post-treatment enhance their protective effect by the formation of corrosion product layers.
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.
This specification describes how corrosion monitoring is used to check the condition of reinforced and prestressed concrete members. In this specification, the term "corrosion monitoring" covers all methods in which it is possible to continuously track corrosion-relevant variables in the area of stationary, built-in sensors. This specification does not cover other possible methods, such as potential field measurements, involving the use of mobile, portable sensors that are placed temporarily on the membersurface to take measurements.
Die Potentialmessung kann zum Auffinden korrosionsaktiver Bereiche neben Stahlbetonbauwerken auch bei Spannbetonbauwerken angewandt werden, die mit Spannstählen im direkten Verbund hergestellt werden. Bei Vorspannsystemen mit metallischen Hüllrohren im nachträglichen Verbund ist eine Aussage über den Korrosionszustand des Hüllrohrs, nicht aber des Spannstahls möglich. Messungen an Spannbetonbauteilen erfordern grundsätzlich die besonderen Kenntnisse eines Spezialisten.
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.
Stainless steel AISI 304 surfaces were studied after a mild anodic polarization for oxide growth in the presence and absence of two derivatives of vitamin B2 (riboflavin and flavin mononucleotide) that can be secreted by metal‐reducing bacteria and act as a chelating agent for iron species. The alterations in oxide chemistry were studied by means of surface‐sensitive techniques such as X‐ray photoelectron spectroscopy and time‐of‐flight secondary ion mass spectrometry analysis. The complementary electrochemical characterization revealed a preferential growth of an oxide/hydroxide iron‐rich film that is responsible for an altered pit initiation and nucleation behavior. These findings suggest that as the corrosion behavior is determined by the interplay of the chemical and electronic properties, only a mild anodic polarization in the presence of redox‐active molecules is able to alter the chemical and electronic structure of the passive film formed on stainless steel AISI 304. This helps to achieve a profound understanding of the mechanisms of microbially influenced corrosion (MIC) and especially the possible effects of the redox‐active biomolecules, as they may play an important role in the corrosion susceptibility of stainless steel surfaces.
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.
Al2O3 has been widely used as a coating in industrial applications due to its excellent chemical and thermal resistance. Considering high temperatures and aggressive mediums exist in geothermal systems, Al2O3 can be a potential coating candidate to protect steels in geothermal applications. In this study, γ-Al2O3 was used as a coating on martensitic steels by applying AlOOH sol followed by a heat treatment at 600 °C. To evaluate the coating application process, one-, two-, and three-layer coatings were tested in the artificial North German Basin (NGB), containing 166 g/L Cl−, at 150 °C and 1 MPa for 168 h. To reveal the stability of the Al2O3 coating in NGB solution, three-layer coatings were used in exposure tests for 24, 168, 672, and 1296 h, followed by surface and cross-section characterization. SEM images show that the Al2O3 coating was stable up to 1296 h of exposure, where the outer layer mostly transformed into boehmite AlOOH with needle-like crystals dominating the surface. Closer analysis of cross-sections showed that the interface between each layer was affected in long-term exposure tests, which caused local delamination after 168 h of exposure. In separate experiments, electrochemical impedance spectroscopy (EIS) was performed at 150 °C to evaluate the changes of coatings within the first 24 h. Results showed that the most significant decrease in the impedance is within 6 h, which can be associated with the electrolyte penetration through the coating, followed by the formation of AlOOH. Here, results of both short-term EIS measurements (up to 24 h) and long-term exposure tests (up to 1296 h) are discussed.
The chapter starts with a brief introduction about corrosion, which is defined as the interdependency between a metal, a corrosive environment, and the respective component design. The second section introduces the most important forms of aqueous electrochemical corrosion (uniform corrosion, galvanic corrosion, selective and intergranular corrosion, and finally pitting and crevice corrosion in the case of passive layer forming metals). In addition, electrochemical corrosion under applied mechanical load is introduced (stress corrosion cracking, hydrogen-assisted cracking, corrosion fatigue), as well as special forms of corrosion (erosion, fretting, and microbiologically induced corrosion). The third section of this chapter introduces (mostly dry) chemical corrosion and high-temperature corrosion (oxidation, carburization, high-temperature hydrogen attack, sulfurization, nitriding, halogenation). As in the case of electrochemical corrosion, chemical corrosion can also be superimposed by mechanical loads. Finally, general facts on the testing of corrosion are introduced.
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.
For reliability and safety issues of injection wells, corrosion resistance of materials used needs to be determined. Herein, representative low-cost materials, including carbon steel X70/1.8977 and low alloyed steel 1.7225, were embedded in mortar to mimic the realistic casing-mortar interface. Two types of cement were investigated: (1) Dyckerhoff Variodur commercial Portland cement, representing a highly acidic resistant cement and (2) Wollastonite, which can react with CO2 and become stable under a CO2 stream due to the carbonation process. Exposure tests were performed under 10 MPa and at 333 K in artificial aquifer fluid for up to 20 weeks, revealing crevice corrosion and uniform corrosion instead of expected pitting corrosion. To clarify the role of cement, simulated pore water was made by dispersing cement powder in aquifer fluid and used as a solution to expose steels. Surface analysis, accompanied by element mapping on exposed specimens and their crosssections, was carried out to trace the chloride intrusion and corrosion process that followed.
Geothermal brines often contain high amounts of lead and copper ions that can precipitate as native Cu and Pb as consequence of galvanic corrosion when brines react with carbon steel materials. This contribution evaluates which materials could overcome the problem of galvanic corrosion at geothermal environment.
The behavior of these materials in water containing high chloride concentration (> 100 g/L NaCl) as well as various amounts of dissolved bCl2 and/or CuCl2 was characterized by electrochemical and exposure measurements.
Both methods reveal carbon steel suffers corrosion susceptibility, accompanied by Cu◦ and/or Pb◦ precipitation on the surface. Electrochemical measurements on stainless steels result in significant difference in corrosion and repassivation potentials (Ecorr = -189 mV, Erep = 70 mV), indicating a good corrosion resistance.
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.
Since data processing has now also found its way into materials science, there has been a great demand from users for a corresponding textbook. This book provides a guide to the latest advances of materials informatics and data mining for materials science. 46 authors introduce readers to methods, present tools and case studies to illustrate the power of materials informatics within this new field of application.
This paperback issue of the 2007 hardcover version within the “Corrosion Engineering Handbook” series presents various materials and methods for controlling and protecting against corrosion instead of using expensive alloys to construct a tank or processing vessel.
This book is a very comprehensive collection of the current knowledge about applied linings and coatings. So, it fulfills its intension, “that regardless of what is being built, … information for … whoever is responsible for the selection of material of construction will be found in this book to enable them to avoid unnecessary loss of material through corrosion”, to a very large extent.
Polyaniline/Silicon Dioxide Composite-Based Coating for Corrosion Protection in Geothermal Systems
(2020)
Geothermal energy is one of the cleanest renewable alternatives to reduce the dependency on fossil fuel [1, 2]. Despite its promising future, its implementation faces various challenges, one of them being corrosion processes. To implement this energy, hot fluids are pumped from a geothermal well. These hot fluids originate from deep within the earth, so consist of different ionic species and gases in a wide range of temperatures, which lead to their corrosive nature. In terms of geothermal energy resources, Indonesia is at the forefront, with the highest preserved geothermal energy in the world of about 29 GWe and 312 potential geothermal locations [3]. Geothermal wells in Sibayak (North Sumatera), Indonesia, belong to young stratovolcanoes and have operating temperatures varying from 36 °C at the near ground surface to 310 °C at the bottom of the well, which is liquid-dominated with acidic and saline properties [4, 5]. Therefore, this geothermal fluid creates an aggressive environment that is conducive to corrosion of the powerplant infrastructure.
Parts of the geothermal powerplant infrastructure, such as pipelines and heat exchangers, are commonly made of metals, e.g. carbon steel and stainless steel. Consequently, they may undergo corrosion and scaling when exposed to the geothermal fluid, especially for carbon steel. To ensure the safety and longevity of a geothermal powerplant, the infrastructure is constructed of expensive corrosion resistant alloys [6–10], e.g., titanium and Ni-Cr based alloys, or carbon steel which needs to be protected by coatings or inhibitors.
To address the corrosion of carbon steel in the geothermal environment, artificial geothermal water was used to simulate a geothermal well in Sibayak, Indonesia, with pH 4 and a saline 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+. Carbon steel underwent the most severe corrosion at 150°C in an oxygen-containing solution with a corrosion rate of 0.34 mm/year, which is approximately ten times higher than that in the absence of dissolved oxygen. In all conditions, pitting corrosion was observed, which necessitate a protection strategy on carbon steel. In order to promote a cost effective and locally available option, this work focused on an easily applicable coating which utilized local resources.
Toward developing such protective coating based on the locally available resources in Indonesia which can yield good corrosion resistance and thermal stability in geothermal environment, two additional components, i.e. polyaniline (PANI) and silicon dioxide, were used to modify an alkyd-based commercial coating. The selection of the alkyd-based coating as a matrix focused on the industrial convenience basis, where the coating application procedure should be simple and easy to apply within reasonable costs. The alkyd-based coating underwent severe blistering when exposed to the artificial geothermal water at 70 and 150°C due to the reaction between CaCO3 (as one of its components) and the artificial geothermal water, as well as a possible alkyd hydrolysis in the initial stage of exposure. In the oxygen-free solution, the degradation was controlled by chemical and thermal reactions, whereas in the aerated condition, oxidization at the coating surface further accelerated polymer degradation.
PANI was chosen as one of the anticorrosion pigments which was widely developed over the past decades. To investigate the interaction between PANI and the artificial geothermal water, PANI film was electrochemically deposited on the carbon steel surface and exposed to the artificial geothermal water. Electrochemically synthesized oxalate-doped PANI was protective against corrosion of carbon steel in artificial geothermal water at room temperature. The mechanism involved an exchange of electroactive species within the coating layer, as confirmed by electrochemical impedance spectra. Interaction of ionic species, such as Cl-, Na+, Ca2+ from the artificial geothermal water, with the outer layer of PANI is suggested both at 25°C and 150°C, based on the EDX spectra of the coating surface after exposure to the artificial geothermal water. Thus, the protection mechanism of PANI is not solely based on the physical barrier layer properties, but rather associated with the redox mediated properties of PANI, which selectively allow ionic species intrusion from the electrolyte into the PANI layer. Although PANI is a promising candidate as an anticorrosion coating, its morphological characterization reveals that electrochemically deposited PANI is not stable for an application at 150°C. Therefore, another approach was used to promote better protective behavior of PANI by dispersing chemically synthesized PANI in the alkyd-based coating.
To enhance the thermal stability of the coating, silicon dioxide (SiO2) was added, which was able to prolong the sustainability of coated metals until 28 days compared to the unmodified alkyd-based coating, which underwent a change in color to brown/orange only within 7 days of exposure. This improvement might be associated with the role of SiO2 to proportionate the thermal expansion coefficient of the coating system to be compatible with that of carbon steel. Although the coating is thermally enhanced, the electrolyte might still intrude through the coating resulting in the change of coating color after 28 days of exposure in the artificial geothermal water. When PANI was added, the coating system provided an active corrosion protection on the carbon steel surface. The chemical and morphological characterization of the PANI-alkyd and SiO2-alkyd coating system showed that coatings were improved, and no blisters were observed, albeit the degradation continued. Based on the results of exposure tests, the combined coating system was further investigated.
The combinational coating of PANI/SiO2-alkyd was used with 2 wt% of PANI and 15 wt% of SiO2. Electrochemical tests indicated cathodic protection at 150°C, as the Ecorr of PANI/SiO2 remained approximately 400 mV lower than the carbon steel potential. The impedance spectra of the combinational coating of PANI/SiO2 showed a continuous decrease in the absolute impedance value over time. A significant decrease was observed within one day of exposure, followed by a slow gradual decrease, which might be associated with water absorption in the coating. FTIR spectra revealed that several peaks associated with the organic portion of the coatings were reduced after the specimens were exposed for 6 months. However, the absorption peaks related to the inorganic portion of the coatings remained stable until 6 months. Morphological characterization of the combinational coating of PANI/SiO2 showed that there were no blisters or significant discoloration of coatings after long-term exposure for 6 months in artificial geothermal water at 150°C, indicating that the chemical degradation does not significantly affect the functionality of the coating. This clearly shows the durability of PANI/SiO2 coating in the geothermal condition, suggesting that this coating can be used for such geothermal application. However, further testing of this coating should be conducted in a real geothermal environment on-site to ensure safety and viability.
Detektion korrosionsaktiver Bereiche an Brückenbauwerken aus Stahlbeton mittels Potentialfeldmessung
(2020)
Durch das alkalische Porenwassermilieu wird Stahl im Beton durch Ausbildung einer Deckschicht vor Korrosion geschützt. Unter ungünstigen Umgebungsbedingungen (Karbonatisierung, Chlorideintrag) kann die passive Deckschicht auf der Stahloberfläche zerstört werden. Im weiteren Verlauf können sich durch Volumenexpansion der Korrosionsprodukte korrosionsbedingte Folgeschäden, wie Risse und Abplatzungen am Bauwerk ergeben. Um notwendige Sanierungsmaß-nahmen sind frühzeitige und weitgehend zerstörungsfrei ermittelte Informationen über das aktuelle Korrosionsverhalten der Stahlbewehrung von großer Bedeutung. Die Potentialfeldmessung ist ein etabliertes und weit verbreitetes Verfahren zur Beurteilung des Korrosionszustandes der Bewehrung in Stahlbetonbauwerken. Mit Hilfe dieses Verfahrens können Bereiche aktiv korrodierender Bewehrung zerstörungsfrei lokalisiert werden. In der Regel kommt diese Messmethode bei der Detektion chloridinduzierter Korrosion zum Einsatz.
High-entropy alloys (HEAs) are characterized by a solid solution of minimum five and medium-entropy alloys (MEAs) of minimum three principal alloying elements in equiatomic proportions. They show exceptional application properties, such as high-strength and ductility or corrosion resistance. Future HEA/MEA-components could be exposed to hydrogen containing environments like vessels for cryogenic or high-pressure storage where the hydrogen absorption and diffusion in these materials is of interest. In our study, we investigated the HEA Co20Cr20Fe20Mn20Ni20 and the MEA Co33.3Cr33.3Ni33.3. For hydrogen ingress, cathodic charging was applied and diffusion kinetic was measured by high-resolution thermal desorption spectros-copy using different heating rates up to 0.250 K/s. Peak deconvolution resulted in high-temperature desorption peaks and hydrogen trapping above 280 °C. A total hydrogen concentration > 40 ppm was identified for the MEA and > 100 ppm for HEA. This indicates two important effects: (1) delayed hydrogen diffusion and (2) considerable amount of trapped hydrogen that must be anticipated for hydrogen assisted cracking phenomenon. Local electrochemical Volta potential maps had been measured for the hydrogen free condition by means of high-resolution Scanning Kelvin Probe Force Microscopy (SKPFM).
This book introduces to aspects to be considered when dealing with coatings and linings. Philip A. Schweitzer covers and compares a variety of specific coatings and their applications. In 18 chapters he divided the content into two main parts: linings and coatings.
All professionals involved in design and maintenance processes get by this book a compact survey of necessary considerations which needs to be done when applying surface protection measures. The literature references at the end of some chapters support the readers finding additional information about the special topic, mainly written by the author himself. Since this newly issued paperback edition is a 1:1 re‐print of the 2001 hardcover version, neither current publications are referenced, nor revisions were made.
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.
Literature data on the influence of concrete cracks on corrosion propagation of reinforcing steel are contradictory. This might be due to very different exposure and test conditions but also to a lack of time-resolved data in cyclic wetting–drying exposure. Here, the influence of the environmental conditions on the corrosion rates in cracked concrete is studied experimentally. The results show that the corrosion rate in cracked concrete depends on the duration of wetting and drying phases and the relative humidity (RH) during the drying phase. The lower the ambient RH in the drying phase, the faster the cracks dry, which depresses the corrosion rate in the periods between the wetting events. A model is proposed to estimate corrosion rates in cracked concrete cyclic wetting/drying exposure.
In 2019 CRC Press published the “Concrete Repair to EN 1504” as paperback. This issue does not differ in terms of content from the hardback publication of 2014. Like the previous version, the book covers both detailed background information on repair procedures of reinforced concrete structures and provides a reference work for technicians and people who are involved with the maintenance of these structures, according to EN 1504.
The book presents a high number of figures and tables, i.e., approximately one illustration per page.
For readers who prefer a more comfortable to handle paperback, the book is recommended; however, the hardback from 2014 is still up‐to‐date.
This edition, published as first issue within the series “Corrosion Atlas”, provides 181 corrosion case studies, collected from 29 contributors.
These Corrosion Atlas Case Studies provide a helpful tool required for engineers in their daily life to quickly determine and solve their equipment's corrosion problems by compact theoretical background and vivid examples. It fulfills the intension of the editors to be “the first centralized collection of case studies containing challenges paired directly with solutions together in one location”.
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.
Early Stage of Corrosion Formation on Pipeline Steel X70 Under Oxyfuel Atmosphere at Low Temperature
(2020)
The early stage of corrosion formation on X70 pipeline steel under oxyfuel atmosphere was investigated by applying a simulated gas mixture (CO2 containing 6700 ppmv O2, 100 ppmv NO2, 70 ppmv SO2 and 50 ppmv H2O) for 15 h at 278 K and ambient pressure. Short-term tests (6 h) revealed that the corrosion starts as local spots related to grinding marks progressing by time and moisture until a closed layer was formed. Acid droplets (pH 1.5), generated in the gas atmosphere, containing a mixture of H2SO4 and HNO3, were identified as corrosion starters. After 15 h of exposure, corrosion products were mainly X-ray amorphous and only partially crystalline. In-situ energy-dispersive X-ray diffraction (EDXRD) results showed that the crystalline fractions consist primarily of water-bearing iron sulfates. Applying Raman spectroscopy, water-bearing iron nitrates were detected as subordinated phases. Supplementary long-term tests exhibited a significant increase in the crystalline fraction and formation of additional water-bearing iron sulfates. All phases of the corrosion layer were intergrown in a nanocrystalline network. In addition, numerous globular structures have been detected above the corrosion layer, which were identified as hydrated iron sulphate and hematite. As a type of corrosion, shallow pit formation was identified, and the corrosion rate was about 0.1 mma−1. In addition to in-situ EDXRD, SEM/EDS, TEM, Raman spectroscopy and interferometry were used to chemically and microstructurally analyze the corrosion products.
This book by Scrivener Publishing contains 14 chapters written by 82 leading scientists, experienced in the field of coatings. They demonstrate mechanisms, usage and manipulation of cutting‐edge coating methods. Each chapter is well structured and ends with a conclusion, highlighting the content. The book is divided into 3 parts: “Materials and Methods”, “Coating Materials Nanotechnology” and “Advanced Coating Technology and Applications”.
Finally, this book provides a comprehensive insight into innovative research in advanced coating materials and state‐of‐the‐art technologies, without being a real textbook. It fulfills its intension of being beneficial both for technicians and scientists.
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.
This concise reference book,consisting of 2 volumes, provides “key scientific and technical properties and data” for “materials scientists, metallurgists, engineers,chemists, and physicists as well as academic staff, technicians, and students” dealing with such kind of materials.
Within its 3rd edition the previous work was extended by a chapter on occupational health and safety issues of materials, beside of the update of whole content. Within 22 chapters materials properties and data are summarized in many tables. Some facts are illustrated by drawings and diagrams for better understandability. Each chapter ends with a part on further reading arranged accordingly.
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.
This book grew out of a course on polymer coatings held by the author at the university. It shall serve as an introduction to the wide field of polymer coatings. It is not intended to cover completely all facts on polymer coatings.
All chapters are well structured. Selected figures and formulas illustrate the content and contribute to a good understandability. At the end of each chapter some hints for further reading are provided.
Finally, the book fulfills its intention to introduce into the topic by providing basics on science and technology of polymer coatings, suitable for chemists in industry, materials scientists, polymer chemists and physical chemists.
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 .
Roaldite – Fe4N – has been identified in the São Julião de Moreira iron meteorite using electron backscatter diffraction (EBSD) and simultaneously acquired energy-dispersive x-ray spectroscopy (EDS). Mean-periodic-number images derived from raw EBSD patterns confirm this phase by an even higher spatial resolution compared to EDS.
Roaldite appears in the form of systematically and repetitively aligned plates. Despite the locally heavy plastic deformation, it is shown that the origin of the oriented precipitation of roaldite is linked to the orientation of the kamacite matrix. Roaldite can be considered to be precipitated from kamacite using an inverse Kurdjumov-Sachs (K-S) or Nishiyama-Wassermann (N-W) orientation relationship. A more accurate discrimination is impossible due to the accumulated shock deformation, which blurs the local reference orientation of kamacite. The habit plane of roaldite is found to be {112}R, which is most likely parallel to {120}K of kamacite. Some of the roaldite plates contain two orientation variants which repeatedly alternate. Their misorientation angle is about 12°.
In civil engineering, many structures are made of reinforced concrete. Most Degradation processes relevant to this material, e.g., corrosion, are related to an increased level of material moisture.
Therefore, moisture monitoring in reinforced concrete is regarded as a crucial method for structural health monitoring. In this study, passive radio frequency identification (RFID)-based sensors are embedded into the concrete. They are well suited for long-term operation over decades and are well protected against harsh environmental conditions. The energy supply and the data transfer of the humidity sensors are provided by RFID. The sensor casing materials are optimised to withstand the high alkaline environment in concrete, having pH values of more than 12. Membrane materials are also investigated to identify materials capable of enabling water vapour transport from the porous cement matrix to the embedded humidity sensor. By measuring the corresponding relative humidity with embedded passive RFID-based sensors, the cement hydration is monitored for 170 days.
Moreover, long-term moisture monitoring is performed for more than 1000 days. The Experiments show that embedded passive RFID-based sensors are highly suitable for long-term structural health monitoring in civil engineering.
The second edition of this textbook on physical electrochemistry, written by two experienced teachers of physical chemistry, corrosion engineering and materials science and engineering, covers the current knowledge which should be transferred to students of these fields.
In 20 chapters the fundamentals of electrochemistry, the most important electrochemical measurement techniques and applications of electrochemistry are covered.
It can be concluded that this study fulfills its intension of “serving as a key textbook in undergraduate courses” dealing with electrochemistry and being “a reference source for graduated students, researchers and engineers” interested in this field. Teachers will find sufficient content for preparing lectures on this topic. Even self‐learning is well supported by the clear structure, presented content and provided sources for further reading.
This study focuses on the corrosion mechanism of carbon steel exposed to an artificial geothermal brine influenced by carbon dioxide (CO2) gas. The tested brine simulates a geothermal source in Sibayak, Indonesia, containing 1500 mg/L of Cl-, 20 mg/L of SO4 2-, and 15 mg/L of HCO3-with pH 4. To reveal the temperature effect on the corrosion behavior of carbon steel, exposure and electrochemical tests were carried out at 70 °C and 150 °C. Surface analysis of corroded specimens showed localized corrosion at both temperatures, despite the formation of corrosion products on the surface. After 7 days at 150 °C, SEM images showed the formation of an adherent, dense, and crystalline FeCO3 layer. Whereas at 70 °C, the corrosion products consisted of chukanovite (Fe2(OH)2CO3) and siderite (FeCO3), which are less dense and less protective than that at 150 °C.
Control experiments under Ar-environment were used to investigate the corrosive effect of CO2. Free corrosion potential (Ecorr) and electrochemical impedance spectroscopy (EIS) confirm that at both temperatures, the corrosive effect of CO2 was more significant compared to that measured in the Ar-containing solution. In terms of temperature effect, carbon steel remained active at 70 °C, while at 150 °C, it became passive due to the FeCO3 formation. These results suggest that carbon steel is more susceptible to corrosion at the near ground surface of a geothermal well, whereas at a deeper well with a higher temperature, there is a possible risk of scaling (FeCO3 layer). A longer exposure test at 150 °C with a stagnant solution for 28 days, however, showed the unstable FeCO3 layer and therefore a deeper localized corrosion compared to that of seven-day exposed specimens.
Today glass is broadly used in modern architecture. For indoor applications it is possible to produce decorated glass by using enamel colours and glass painting techniques without any problems. However, this is more limited for applications out of doors. Humidity and environmental pollution attack the surface of the coating and can damage it. There are only a few colours on the market which are resistant towards acids and bases until now. Additionally, most of those colours are opaque. To extend the colour palette, chemically resistant low melting coloured glasses are being developed which are transparent and intensively toned even in thin coating thicknesses. To achieve such an ambitious aim, many parameters have to combine and act in a complex manner. New compositions of lead borosilicate, zinc borosilicate and lead-zinc borosilicate glasses were produced and milled as powder. The thermal properties as well as the environmental stability were analysed. The influence of PbO and ZnO on the thermal properties and the environmental stability were investigated. Evaluation of the fusing results shows that the production and mixture of transparent vitreous enamels for the exterior side of glasses is possible. The tests made it clear that the original materials for making the vitreous enamels must be excellently ground and prepared to achieve a satisfactory result. The method to produce durable vitreous enamels for exterior application also seems to allow the production of glass colours.
This work presents machine learning-inspired data fusion approaches to improve the non-destructive testing of reinforced concrete. The principal effects that are used for data fusion are shown theoretically. Their effectiveness is tested in case studies carried out on largescale concrete specimens with built-in chloride-induced rebar corrosion. The dataset consists of half-cell potential mapping, Wenner resistivity, microwave moisture and ground penetrating radar measurements. Data fusion is based on the logistic Regression algorithm.
It learns an optimal linear decision boundary from multivariate labeled training data, to separate intact and defect areas. The training data are generated in an experiment that simulates the entire life cycle of chloride-exposed concrete building parts. The unique possibility to monitor the deterioration, and targeted corrosion initiation, allows data labeling.
The results exhibit an improved sensitivity of the data fusion with logistic regression compared to the best individual method half-cell potential.
An important aspect with regard to the service life of zinc based galvanic anodes and the durability of the corrosion protection of steel in concrete is the “galvanic chloride extraction”. Chloride ions move in the electric field generated by the current, flowing between the galvanic anode and the cathodic steel. Migration leads to an accumulation of anions, e.g. chloride ions, at the anode and depletion of chlorides near the steel rebar surface. The ion migration was studied on steel reinforced concrete specimens admixed with 3 wt.% chloride/wt. cement and galvanically protected by a surface applied embedded zinc anode (EZA). The zinc anode was embedded and glued to the concrete surface by a geo-polymer based chloride free binder. The EZA was operated over a period of 1 year and the ion distribution between anode (EZA) and cathode (steel reinforcement) was studied by laser induced breakdown spectroscopy (LIBS) after 5 months, 7 months and 12 months. The results show that chloride ions efficiently migrate in the direction of the zinc-anode and accumulate there. Chloride distribution in the EZA correlates with the distribution of zinc ions generated by the anodic dissolution of the zinc anode in the binder matrix. The microstructure of the binder matrix and its interface to the zinc-anode are studied by REM/EDX – preliminary results will be reported.