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The corrosion behavior of galvanized steels and zinc components under atmospheric exposure depends mostly on the corrosion product‐based cover layer formation under the prevailing conditions. The use of agar‐based gel electrolytes makes it possible to use electrochemical methods to obtain a characteristic value from these cover layers that describe their current and future protective capacity. It is shown here that different states of galvanized steel can be distinguished very well under laboratory conditions and that this method is also suitable for use under practical conditions. Based on the characteristic values and assuming future time of wetness, it is very easy to draw up a forecast for the future corrosion rate, which provides plausible values.
It is well known that cement manufacture, including CaCO3 calcination and clinker formation, is associated with substantial energy consumption and significant greenhouse gas emissions. Alkali-activated binders (AAB) and concretes made from them can significantly contribute to reducing CO2 emissions caused by the construction industry. However, to what extent and for how long concretes made from AAB can protect the steel in reinforced concrete components from corrosion is still unclear. Unlike PC-based binders, AABs are made by reacting alkaline solutions with solid precursors such as fly ash and ground granulated blast furnace slag (GGBFS). Therefore, steel reinforcement corrosion mechanisms in AAMs differ from PC-based binders. The present study aims to evaluate the corrosion behavior of steel rebar in alkali-activated materials (AAMs) synthetic pore solution with different chemical concentrations representing different GGBFS and Flay Ash based binders by performing electrochemical tests to measure the corrosion rate and corrosion potential of steel rebar. This information can be used to improve the design of AAMs in order to ensure a longer service life for these materials.
In the late 1980s, a new type of corrosion appeared in drinking water installations where galvanized steel pipes failed forming a deep groove with no corrosion at the other surfaces. The reason was discussed quite fiercely between failure analysts and material suppliers. In the end the discussion lead to the solution: inductive welded pipes of a certain sulphur content were prone to selective corrosion. The history of the arguments is discussed using old communications between Wilhelm Schwenk and Wolfgang Stichel, who later published the results in a paper unfortunately only I german.
Thus the knowledge got lost and new cases based on the same material problems are observed in application of so-called C-Steel piping systems. Failure cases are shown.
In the late 1980s, a new type of corrosion appeared in drinking water installations where galvanized steel pipes failed forming a deep groove with no corrosion at the other surfaces. The reason was discussed quite fiercely between failure analysts and material suppliers. In the end the discussion lead to the solution: inductive welded pipes of a certain sulphur content were prone to selective corrosion. The history of the arguments is discussed using old communications between Wilhelm Schwenk and Wolfgang Stichel, who later published the results in a paper unfortunately only I german.
Thus the knowledge got lost and new cases based on the same material problems are observed in application of so-called C-Steel piping systems. Failure cases are shown.
Since geothermal wells are a feasible energy source to replace fossil fuel supply, many technologies have been developed to take advantage of geothermal energy. Nevertheless, service conditions in geothermal facilities are in many cases extreme in terms of corrosion due to the chemical composition of hydrothermal fluids and temperatures. Therefore, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of the facilities. During operation of a geothermal research facility in Groß Schönebeck copper and lead effects have been found downhole. Occurring mechanisms and measures to prevent precipitation or scaling needed to be investigated as well as potential influences of such precipitates on corrosion resistance of metallic materials used for equipment.
This contribution deals with the evaluation of the corrosion behavior of carbon steel and corrosion resistant alloys in copper and/or lead containing artificial geothermal water, simulating the conditions in the Northern German Basin.
The behavior of these materials in an artificial geothermal water obtained by electrochemical measurements and exposure tests are presented. While carbon steel exhibits precipitation and deposition, higher alloyed material shows different response to such species and a higher resistance in saline geothermal water.
Basing on these results the suitability of the investigated corrosion resistant alloy is given for use in such conditions, whereas carbon steel creates difficulties due to its susceptibility to Cu- and Pb-precipitation.
Significant Cu-deposition and precipitation only occurred in combination with carbon steel. High-alloyed materials prevent the disturbing Cu-agglomeration. Pb-deposition and precipitation only occurred in combination with carbon steel. No negative Pb-effect could be observed in combination with high-alloyed steels. High alloyed corrosion resistant alloys are suitable and shall be chosen for future design of the piping system, either in massive or in cladded form, to prevent unwanted interactions with brine components.
Corrosive geothermal brines are a major challenge to geothermal power-plants. For cost reasons, plant designers favorize low alloyed steels, e.g., carbon steel, which are susceptible to uniform and localized corrosion when exposed to geothermal brines having acidic and saline properties. To solve such problem, coatings or inhibitors would be a protective solution as an alternative to the use of high alloyed materials.
This study investigated a coating system consisting of polyaniline/silicon dioxide basing on locally available resources. Protection against corrosion of carbon steel is shown by long-term exposure and electrochemical tests of coated carbon steels, performed in an artificial acidic and saline geothermal brine, comparable to real conditions at a site in Indonesia.
Therefore, an integrated coating system is presented for corrosion protection, combining the electro-chemical functionality of polyaniline and the physical advantages of silica.
The screening of coatings shows that the modification by adding individual pigment was not sufficient to protect carbon steel even during a short-term exposure, indicated by the discoloration after only seven days of exposure.
Electrochemical tests indicated that the coating cathodically protects carbon steel or slows down the corrosion reaction.
A long-term exposure test confirmed that the PANI/SiO2 modified coating successfully protects the carbon steel in the Sibayak artificial geothermal water at 150 °C for 6 months.
Determination of the corrosion product layer resistance on zinc samples by using gel electrolytes
(2022)
Crash barriers, railings, lamp posts, waste glass containers - these are just a few of the many examples of galvanized surfaces. They withstand wind and weather for decades, which is possible thanks to a protective layer made of corrosion products. When designing the atmospheric durability of galvanized components, a linear corrosion loss is assumed. In the past 30 years, however, the surrounding atmosphere has changed a lot. Due to the restriction of sulfur exhaust air, acid rain completely disappeared in Europe and Germany, which has a direct influence on the type and protective effect of the corrosion products. Under the influence of current atmospheric conditions, zinc layers are significantly more resistant and no longer show any linear corrosion loss. The established test methods cannot correctly map this change in neither short-term nor long-term tests and thus provide incorrect results. In order to solve this problem, a new measurement method was developed at BAM that can assess the protective effect of the formed surface layers in a minimally invasive manner without damaging the sample and in short test times. For this new method, gel electrolytes are used and the so-called corrosion product layer resistance RL, which is made up of various surface resistances, is measured electrochemically. As a single measurement, the surface layer resistance can provide information about the existing corrosion protection, while time-dependent measurements assess the stability of the layer. Thus, it is possible again to evaluate the corrosion protection layer. Furthermore, this method can also be used for field measurements on real components.
To reveal the corrosion resistance of casing steel/mortar interface in CO2 injection condition, sandwich samples were prepared and exposed up to 20 weeks in aquifer fluid under 10 MPa and 60 °C. Cross section analysis revealed the crevice corrosion as main mechanism instead of pitting corrosion, which would be expected to happen in the extremely high Chloride concentration. Detailed analysis using EDS line scan shown the slow diffusion of Chloride, suggesting why pitting did not happen after 20 weeks. To mimic the passivated steel surface, the steel coupon was passivated in simulated pore solution having pH 13.5 for 42 days. The passivated coupon was further exposed to NGB solution for 28 days. Electrochemical characterization was performed along the exposure processes to reveal the change in impedance, indicating the corrosion resistance of steel casing/mortar interface.
Significant Cu-deposition and ‑precipitation only occurred in combination with carbon steel. High-alloyed materials prevent the disturbing Cu-agglomeration. Pb-deposition and ‑precipitation only occurred in combination with carbon steel. No negative Pb-effect could be observed in combination with high-alloyed steels. High alloyed corrosion resistant alloys are suitable and shall be chosen for future design of the piping system, either in massive or in cladded form, if formation of crevices with non-metallic materials can be excluded!
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.
The presentation shows systematic investigations to describe the corrosion and corrosion product formation processes of pure zinc under the climatic conditions currently prevailing in the Federal Republic of Germany. The investigations in their entirety aim at questioning current and establishing new ways of looking at the formation of corrosion products of pure zinc under atmospheric corrosion conditions. Thus, they make a significant contribution in understanding corrosion protection by zinc and zinc coatings. In particular, the focus is placed on the initial stage of the corrosion product formation. A systematic investigation of this time range, which is characterized by very reactive corrosion products, is only made possible by using gel-type electrolytes. The short periods of time at the beginning of weathering is now measurable and their influence on the formation of corrosion products and the kinetics of layer formation describable. By combining the new electrochemical approach with gravimetric, microscopic and analytical methods, new insights could be gained both on a methodic and scientific level.
Commercially available carbon steels are suitable for compression and pipelines as long as moisture content and impurities are limited. (water 50 to 100 ppmv, SO2 and NO2 ca. 100 ppmv) Corrosion rates increase with increasing water content. (0.2 – 20 mm/a) Condensation of acids and therefore droplet formation is always possible, even at low water contents. A low SO2 content within the CO2-stream might be more important than a low water content. Cr13-steels showed a general susceptibility to shallow pitting and pitting. So, they seem to be not suitable for CCUS applications. Low alloyed steels showed better corrosion behavior (predictable uniform corrosion). For direct contact with saline aquifer fluids only high alloyed steels shall be used.
Evaluation of corrosion resistance of metallic materials is essential to assure safe and reliable operation of geothermal sites. One need to be aware that corrosion is not a material's but a system property, determined by medium, material and construction aspects. Various corrosion types have to be evaluated. Conditions in laboratory shall reflect on-site reality. Depending on brine composition and temperature suitability of metallic materials can be ranked. Most important outcome of the research is that highly saline geothermal brines require high alloyed materials, for safe long-term operation.
Integrated Coating System for Corrosion Protection of Carbon Steel in Artificial Geothermal Brine
(2022)
Corrosive geothermal brines are a major challenge to geothermal power-plants. For cost reasons, plant designers prefer to use carbon and low alloyed steels, which are susceptible to uniform and localized corrosion when exposed to geothermal brines having acidic and saline properties. To solve such problem, coatings or inhibitors would be a protective solution as an alternative to the use of high alloyed materials.
This study investigated a coating system consisting of polyaniline/silicon dioxide based on resources locally available in Indonesia. Protection against corrosion of carbon steel was shown by long-term (28 day) exposure and electrochemical tests of coated carbon steels, performed in an artificial acidic and saline geothermal brine, comparable to the conditions encountered at a site in Indonesia.
Therefore, an integrated coating system is proposed for corrosion protection, combining the electrochemical functionality of polyaniline and the physical advantages of silica.
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.
Analyzing the performance of discrete galvanic anode systems using electrochemical investigations
(2021)
Corrosion of reinforcement is one of the major reasons in questioning the service life of building structures. The application of cathodic protection techniques plays a big role in controlling the corrosion process to ensure a longer service life of building structures. This systematic study compares the efficiency and durability of various discrete galvanic zinc anode systems available in the current market using different criteria for measuring efficiency such as potential measurements, electrolyte resistance measurements and several polarization methods to determine the polarizability of the anodes. The results to validate the performance of long-time exposure of discrete zinc anodes in concrete medium are discussed.
The presentation shows systematic investigations to describe the corrosion and corrosion product formation processes of pure zinc under the climatic conditions currently prevailing in the Federal Republic of Germany. The investigations in their entirety aim at questioning current and establishing new ways of looking at the formation of corrosion products of pure zinc under atmospheric corrosion conditions. Thus, they make a significant contribution in understanding corrosion protection by zinc and zinc coatings. In particular, the focus is placed on the initial stage of the corrosion product formation. A systematic investigation of this time range, which is characterized by very reactive corrosion products, is only made possible by using gel-type electrolytes. The short periods of time at the beginning of weathering is now measurable and their influence on the formation of corrosion products and the kinetics of layer formation describable. By combining the new electrochemical approach with gravimetric, microscopic and analytical methods, new insights could be gained both on a methodic and scientific level.
The collaborative project “Impacts of impurities in CO2 streams captured from different emitters in a regional cluster on transport, injection and storage (CLUSTER)” aimed to set up recommendations on how to define “reasonable minimum composition thresholds” that CO2 streams should meet when accessing CO2 transport pipeline networks. Within CLUSTER, we investigated potential impacts of CO2 streams with different and temporally variable compositions and mass flow rates along the whole CCS chain. Investigations included, amongst others, impacts on:
• corrosion of pipeline steel,
• pipeline network design and related transport costs,
• alteration of well bore cements,
• pressure development and rock integrity,
• geochemical reactions, and
• petrophysical and geomechanical rock properties.
All investigations are based on a generic CCS chain scenario. In this scenario, CO2 streams are captured from a spatial cluster of eleven emitters and collected in a regional pipeline network. Emitters comprise seven fossil fuel-fired power plants equipped with different capture technologies, two cement plants, one refinery and one integrated iron and steel plant. In total, 19.78 Mio t CO2 (including impurities) are captured in the emitter cluster annually. The combined CO2 stream is transported in a trunk line with a length of 400 km (100 km of these offshore) and is injected into five generic storage structures. The storage reservoirs are saline aquifers of the Buntsandstein.
The investigations revealed beneficial and deteriorating impacts of different impurities and combinations thereof. Overall, no fundamental technical obstacles for transporting, injecting and storing CO2 streams of the modelled variable compositions and mass flow rates were observed. Based on the results, the CLUSTER project team recommends not to define “minimum composition thresholds” for CO2 streams as strict threshold values for each individual impurity in the stream. Instead, CO2 stream compositions and variabilities for specific CCS projects should be constrained with regard to a set of parameters including i) the overall CO2 content, ii) maximum contents of relevant impurities or elements, iii) acceptable variability of CO2 stream composition, and iv) impurity combinations to be avoided.
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.
Study of Polyaniline/Silicon Dioxide based Coating on Carbon Steel in Artificial Geothermal Brine
(2021)
Geothermal brines are corrosive in nature because of their salt contents and high temperatures. Therefore, they pose a major challenge to geothermal power-plants, which are mostly built of low alloyed steels, e.g., carbon steel. Carbon steel is susceptible to uniform and localized corrosion when exposed to geothermal brines having acidic-saline properties. To overcome this limitation, geothermal power plants should be built by either high alloyed materials or by integrating protection systems on carbon steel, such as coatings and inhibitors. We studied a coating system containing polyaniline/silicon dioxide basing on locally available resources that provides protection against corrosion of carbon steel and enhance the thermal resistance in geothermal environments. Here, exposure and electrochemical tests of coated carbon steels were performed in an artificial geothermal brine. The solution had a pH of 4, with the composition of 1,500 mg/L of chlorides, which is based on the chemical analysis of geothermal brine found in Sibayak, Indonesia. All exposure tests were conducted using autoclaves at 150 °C with a total pressure of 1 MPa, which was performed for up to six months to evaluate the durability of the coating system. Post-experimental analyses were performed by assessing the surface of specimens using optical and electron microscopes. On the other hand, electrochemical tests were performed for seven days at 25 °C and 150 °C to investigate the kinetics of electrochemical reactions by measuring open circuit potential and electrochemical impedance spectra. Experimental results showed the corrosion resistance of PANI/SiO2 composite coatings, where polyaniline and SiO2 play their roles as stabilizers.
Influence of Precipitating Brine Components on Materials Selection for Geothermal Applications
(2021)
Since geothermal wells are a feasible energy source to replace fossil fuel supply, many technologies have been developed to take advantage of geothermal energy. Nevertheless, service conditions in geothermal facilities are in many cases extreme in terms of corrosion due to the chemical composition of hydrothermal fluids and temperatures. Therefore, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of the facilities. During operation of a geothermal research facility in Groß Schönebeck copper and lead effects have been found downhole. Occurring mechanisms and measures to prevent precipitation or scaling needed to be investigated as well as potential influences of such precipitates on corrosion resistance of metallic materials used for equipment.
This contribution deals with the evaluation of the corrosion behavior of carbon steel and corrosion resistant alloys in copper and/or lead containing artificial geothermal water, simulating the conditions in the Northern German Basin.
The behavior of these materials in an artificial geothermal water obtained by electrochemical measurements and exposure tests are presented. While carbon steel exhibits precipitation and deposition, higher alloyed material shows different response to such species and a higher resistance in saline geothermal water.
Basing on these results the suitability of the investigated corrosion resistant alloy is given for use in such conditions, whereas carbon steel creates difficulties due to its susceptibility to Cu- and Pb-precipitation.
Study of Polyaniline/Silicon Dioxide based Coating on Carbon Steel in Artificial Geothermal Brine
(2021)
By using the available resources in Indonesia, such as silicon dioxide and marine coating base, the PANI/SiO2 modified alkyd coating was able to protect carbon steel in a deaerated artificial geothermal water. The screening of coatings shows that the modification by adding individual pigment was not sufficient to protect carbon steel even during a short-term exposure, indicated by the discoloration after only seven days of exposure. Electrochemical tests indicated that there was no significant change in the Ecorr between the coated and uncoated carbon steel at room temperature. At 150 °C, the coated carbon steel has a lower potential than that of carbon steel, indicating that the coating is protecting carbon steel cathodically or slowing down the corrosion reaction. Finally, a long-term exposure test confirmed that the PANI/SiO2 modified coating successfully protects the carbon steel in the Sibayak artificial geothermal water up to 150 °C for 6 months.
Influence of Precipitating Brine Components on Materials Selection for Geothermal Applications
(2021)
By exposure and electrochemical tests in the laboratory the Cu- and Pb-effect on corrosion behavior and performance of carbon steel and a corrosion resistant alloy could be assessed. Critical material specific properties were determined by static exposure and electrochemical tests in artificial geothermal water with high salinity and low pH, containing Cu/Pb.
It could be shown that significant Cu- resp. Pb-deposition and precipitation only occurred in combination with carbon steel. Corrosion resistant alloys (e. g. Cr- and Ni-dominated stainless steels) prevent the disturbing Cu-agglomeration resp. Pb-deposition. Therefore, they are suitable to be chosen for future design of geothermal piping system, either in massive or in cladded form. Regarding corrosion, formation of crevices with non-metallic materials shall be avoided.
So, in addition to its already known limited corrosion resistance, carbon steel shall not be used when copper or lead species are content of the geothermal brine. Otherwise precipitation and/or deposition of metallic copper resp. lead must be expected, increasing the susceptibility of clogging the piping system.
From the interactions and pitting corrosion point of view, corrosion resistant alloys (preferably Ni-rich) seem to be most favorable when selecting materials for applications in such geothermal brines.
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.
The presentation shows systematic investigations to describe the corrosion and corrosion product formation processes of pure zinc under the climatic conditions currently prevailing in the Federal Republic of Germany. The investigations in their entirety aim at questioning current and establishing new ways of looking at the formation of corrosion products of pure zinc under atmospheric corrosion conditions. Thus, they make a significant contribution in understanding corrosion protection by zinc and zinc coatings. In particular, the focus is placed on the initial stage of the corrosion product formation. A systematic investigation of this time range, which is characterized by very reactive corrosion products, is only made possible by using gel-type electrolytes. The short periods of time at the beginning of weathering is now measurable and their influence on the formation of corrosion products and the kinetics of layer formation describable. By combining the new electrochemical approach with gravimetric, microscopic and analytical methods, new insights could be gained both on a methodic and scientific level.
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.
Al2O3 coatings are often used as protective layers on steels against electrochemical and high-temperature corrosion because they are chemically inert and stable at elevated temperatures. This study presents preliminary work on the possibilities of using Al2O3 sol-gel coatings for corrosion protection of martensitic stainless steels in geothermal environments. Al2O3 sol-gel coatings were applied on UNS S42000, which is known to be susceptible to uniform and localized corrosion. The coated steel specimens were then tested in two types of artificial geothermal water, which simulate the geothermal fluids found in Sibayak (SBY), Indonesia, and North German Basin (NGB), Germany, respectively. SBY has pH 4 and 1.5 g/L of chloride ions, whereas NGB has a pH of 6 and 166 g/L of chloride ions. All experiments were carried out in autoclaves at 150 °C and 1 MPa under the deaerated condition. Evaluations were performed by investigating the surface profiles of both uncoated and coated steels before and after the corrosion test using a Laser Scanning Microscope (LSM) and Scanning Electron Microscope (SEM). Finally, Electrochemical Impedance Spectroscopy (EIS) was performed to compare the corrosion resistance of Al2O3 coated steels in SBY and NGB solutions. It was observed from the corrosion test that Al2O3 coatings are more suitable for use in the geothermal water with a higher pH.
Al2O3 coatings are often used as protective layers on steels against electrochemical and high-temperature corrosion because they are chemically inert and stable at elevated temperatures. This study presents preliminary work on the possibilities of using Al2O3 sol-gel coatings for corrosion protection of martensitic stainless steels in geothermal environments. Al2O3 sol-gel coatings were applied on UNS S42000, which is known to be susceptible to uniform and localized corrosion. The coated steel specimens were then tested in two types of artificial geothermal water, which simulate the geothermal fluids found in Sibayak (SBY), Indonesia, and North German Basin (NGB), Germany, respectively. SBY has pH 4 and 1.5 g/L of chloride ions, whereas NGB has a pH of 6 and 166 g/L of chloride ions. All experiments were carried out in autoclaves at 150 °C and 1 MPa under the deaerated condition. Evaluations were performed by investigating the surface profiles of both uncoated and coated steels before and after the corrosion test using a Laser Scanning Microscope (LSM) and Scanning Electron Microscope (SEM). Finally, Electrochemical Impedance Spectroscopy (EIS) was performed to compare the corrosion resistance of Al2O3 coated steels in SBY and NGB solutions. It was observed from the corrosion test that Al2O3 coatings are more suitable for use in the geothermal water with a higher pH.
CO2 quality specifications are not only a matter of CO2 purity (i.e. CO2 content).
The “rest” also matters, in particular contents of reactive impurities affecting material corrosion (and rock alteration).
Also chemical reactions in CO2 stream needs to be considered, in particular when combining CO2 streams of different compositions.
Biodiesel (FAME) from rapeseed is an environmentally friendly alternative to common fossil fuels. It is also suitable to serve as blending component to fuels like heating oil. If the fuel composition is changed, materials compatibility must be guaranteed. Adding polar biodiesel to nonpolar heating oil, changes the blend’s solvency and might cause swelling, extraction and solvation of polymers.
The objective of this research was to investigate the compatibility of polymeric materials, which are commonly used for components in middle distillate facilities, along with blends of heating oil and 20 % biodiesel (B20). For this propose, ACM, HNBR, FKM, PE, PA 6, POM, PUR and PVC were exposed to heating oil and B20 for 42 and 84 days at 40 °C. In addition, the polymers HNBR, FKM, PA, POM and PVC were also exposed at 70 °C. Furthermore, the resistance of polymers in eight-year aged B10 at 40 °C was evaluated. Ageing of biodiesel increases acidity which might propagate polymer corrosion.
The materials were evaluated as resistant, if the loss in tensile properties (tensile strength and elongation at break) and Shore hardness remained under 15 % compared to the initial unexposed material values. For investigations under compressed conditions, the compression set was determined for specimens of ACM, FKM and HNBR after exposure in heating oil B0 and B20 for 3,7,14, 28, 56 and 90 days at 40 °C according to ISO 815-1.
It was found that the resistance in B20 at 40 °C was given for all tested polymers except PUR. In the 8 years aged B10, PUR and POM were not compatible and ACM just conditionally compatible. At 70 °C, FKM and PVC were resistant in B20, whereas HNBR and PA 6 were not compatible. Swelling occurred for the elastomers ACM, HNBR and PUR.
The collaborative project “Impacts of impurities in CO2 streams captured from different emitters in a regional cluster on transport, injection and storage (CLUSTER)” aimed to set up recommendations on how to define “reasonable minimum composition thresholds” that CO2 streams should meet when accessing CO2 transport pipeline networks. Within CLUSTER, we investigated potential impacts of CO2 streams with different and temporally variable compositions and mass flow rates along the whole CCS chain. Investigations included, amongst others, impacts on: Corrosion of pipeline steel, pipeline network design and related transport costs, alteration of well bore cements, pressure development and rock integrity, geochemical reactions, and petrophysical and geomechanical rock properties.
All investigations are based on a generic CCS chain scenario. In this scenario, CO2 streams are captured from a spatial cluster of eleven emitters and collected in a regional pipeline network. Emitters comprise seven fossil fuel-fired power plants equipped with different capture technologies, two cement plants, one refinery and one integrated iron and steel plant. In total, 19.78 Mio t CO2 (including impurities) are captured in the emitter cluster annually. The combined CO2 stream is transported in a trunk line with a length of 400 km (100 km of these offshore) and is injected into five generic storage structures. The storage reservoirs are saline aquifers of the Buntsandstein.
The investigations revealed beneficial and deteriorating impacts of different impurities and combinations thereof. Overall, no fundamental technical obstacles for transporting, injecting and storing CO2 streams of the modelled variable compositions and mass flow rates were observed. Based on the results, the CLUSTER project team recommends not to define “minimum composition thresholds” for CO2 streams as strict threshold values for each individual impurity in the stream. Instead, CO2 stream compositions and variabilities for specific CCS projects should be constrained with regard to a set of parameters including i) the overall CO2 content, ii) maximum contents of relevant impurities or elements, iii) acceptable variability of CO2 stream composition, and iv) impurity combinations to be avoided.
The collaborative project “Impacts of impurities in CO2 streams captured from different emitters in a regional cluster on transport, injection and storage (CLUSTER)” aimed to set up recommendations on how to define “reasonable minimum composition thresholds” that CO2 streams should meet when accessing CO2 transport pipeline networks. Within CLUSTER, we investigated potential impacts of CO2 streams with different and temporally variable compositions and mass flow rates along the whole CCS chain. Investigations included, amongst others, impacts on: Corrosion of pipeline steel, pipeline network design and related transport costs, alteration of well bore cements, pressure evelopment and rock integrity, geochemical reactions, and petrophysical and geomechanical rock properties.
All investigations are based on a generic CCS chain scenario. In this scenario, CO2 streams are captured from a spatial cluster of eleven emitters and collected in a regional pipeline network. Emitters comprise seven fossil fuel-fired power plants equipped with different capture technologies, two cement plants, one refinery and one integrated iron and steel plant. In total, 19.78 Mio t CO2 (including impurities) are captured in the emitter cluster annually. The combined CO2 stream is transported in a trunk line with a length of 400 km (100 km of these offshore) and is injected into five generic storage structures. The storage reservoirs are saline aquifers of the Buntsandstein.
The investigations revealed beneficial and deteriorating impacts of different impurities and combinations thereof. Overall, no fundamental technical obstacles for transporting, injecting and storing CO2 streams of the modelled variable compositions and mass flow rates were observed. Based on the results, the CLUSTER project team recommends not to define “minimum composition thresholds” for CO2 streams as strict threshold values for eachindividual impurity in the stream. Instead, CO2 stream compositions and variabilities for specific CCS projects should be constrained with regard to a set of parameters including i) the overall CO2 content, ii) maximum contents of relevant impurities or elements, iii) acceptable variability of CO2 stream composition, and iv)impurity combinations to be avoided.
“Corrosive to Metals” (H290) describes the general potential danger of a substance to metallic materials. Uniform and localized attack is considered. It has nothing to do with containment material. Corrosion resistance of materials is determined similarly, but with much lower threshold values.
Manual shall provide a simple test to easily determine the aggressivity potential to cause corrosion on metallic materials.
Even a simple test requires experienced personnel. There seems to be a need of awareness and understanding training for both officials and applicants.
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.
The aim of the work presented was the evaluation of corrosion resistance
of various materials in geothermal Waters as a base to create a catalogue of suitable materials for applications in (not only) German geothermal power plants.
Users shall be enabled to have a basis for designing such facilities. High alloyed corrosion resistant alloys are suitable and do not cause copper or lead deposition. They shall be chosen for future design of the piping system, either in massive or in cladded form, if crevices formation with non-metallic materials can be prevented!
Carbon Capture Utilization and Storage (CCUS) is a promising technology to reach the target for reduction of CO2 emissions. Crucial points for a sustainable and future-proof CCUS system are reliability and cost efficiency of the whole process chain, including separation of CO2 from the source, compression of CO2, its subsequent transportation to the injection site and injection into geological formations, e.g. aquifers. Recent studies have shown that even at a very low concentration of impurities, condensation of sulfuric and nitric acids in dense phase CO2 are possible and observable. Thus, impact of impure CO2 stream toward corrosion susceptibility of materials to be used in CCUS system need to be considered. In this talk, basing on results achieved from two German long-term projects (COORAL and CLUSTER), the dominating impurities of the CO2 stream and corrosion mechanisms are addressed. Investigations cover the whole CCUS process chain and provide a material recommendation for certain parts.
Since geothermal wells are a feasible energy source to replace fossil fuel supply, many technologies have been developed to take advantage of geothermal energy. Nevertheless, service conditions in geothermal facilities are in many cases extreme in terms of corrosion due to the chemical composition of hydrothermal fluids and temperatures. Therefore, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of the facilities. During operation of a geothermal research facility in Groß Schönebeck copper and lead effects have been found downhole. Occurring mechanisms and measures to prevent precipitation or scaling needed to be investigated as well as potential influences of such precipitates on corrosion resistance of metallic materials used for equipment.
This contribution deals with the evaluation of the corrosion behavior of carbon steel and corrosion resistant alloys in copper and/or lead containing artificial geothermal water, simulating the conditions in the Northern German Basin.
The behavior of these materials in an artificial geothermal water obtained by electrochemical measurements and exposure tests are presented. While carbon steel exhibits precipitation and deposition, higher alloyed material shows different response to such species and a higher resistance in saline geothermal water.
Basing on these results the suitability of the investigated corrosion resistant alloy is given for use in such conditions, whereas carbon steel creates difficulties due to its susceptibility to Cu- and Pb-precipitation.
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.
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 “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.
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.
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.
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 contribution provides current findings regarding materials susceptibility for carbon capture, utilization and storage (CCUS) applications. Basing on results gathered in 2 German long-term projects (COORAL and CLUSTER) suitable materials are introduced as well as dominating impurities of the CO2-stream and corrosion mechanisms. Investigations cover the whole CCUS process chain and provide material recommendations for certain parts.
This contribution provides current findings regarding materials susceptibility for carbon capture, utilization and storage (CCUS) applications. Basing on results gathered in 2 German long-term projects (COORAL and CLUSTER) suitable materials are introduced as well as dominating impurities of the CO2-stream and corrosion mechanisms. Investigations cover the whole CCUS process chain and provide material recommendations for certain parts.
Susceptibility of 304 stainless steel to crevice corrosion in electrochemically active fluids
(2019)
The susceptibility of AISI 304 stainless steel to crevice corrosion on the effect of contact with electrochemically active fluids was investigated using exposure and stepwise potentiostatic polarisation. Crevice materials made up of 304 SS and Polyether ether ketone (PEEK) forming two kinds of crevices including 304 SS-to-PEEK and 304 SS-to-304 SS were tested.
Susceptibility of 304 stainless steel to crevice corrosion in electrochemically active fluids
(2019)
The susceptibility of AISI 304 stainless steel to crevice corrosion on the effect of contact with electrochemically active fluids was investigated using exposure and stepwise potentiostatic polarisation. Crevice materials made up of 304 SS and Polyether ether ketone (PEEK) forming two kinds of crevices including 304 SS-to-PEEK and 304 SS-to-304 SS were tested.
In Europe biodiesel gained from rapeseeds are considered as an alternative to common fossil fuels due to its environmental performance and its independence from import of raw materials. Biodiesel is also suitable to serve as blending component to heating oil. In that case, it must be considered that changes of fuel composition might cause material degradation.
The objective of this research was to investigate the resistance of metallic materials exposed to heating oil, heating oil blend B20 with 20 % biodiesel and pure biodiesel. Furthermore, the resistance of metals to eight-year aged B10 and six-year aged pure biodiesel was evaluated. Ageing of biodiesel forms acids and water which might propagate metal corrosion. The investigated metals (aluminium, unalloyed steel, austenitic CrNi-steel, copper, die cast zinc and brass) are commonly used for components in middle distillate facilities.
According to DIN 50905-4 the immersed metals were exposed in a climate chamber at 50°C for 4 weeks. The metallic materials were evaluated as resistant if the annual corrosion rate due to uniform corrosion remained under 0.1 mm/year and no localized corrosion in the form of pitting occurred.
The corrosion rates of the exposed materials stayed far below the limit of 0.1 mm/year for all tested fuels. An exception was die cast zinc ZP0410 in eight-year aged B10; a corrosion rate up to 0.3 mm/year due to uniform corrosion was measured. In no case localized corrosion occurred. Copper and brass caused discolouration of biodiesel from yellow to green.
In conclusion, the tested metallic materials were resistant in heating oil, heating oil blend B20 and pure biodiesel at 50 °C. Even the metals exposed to six-year aged biodiesel and eight-year aged B10 showed no uniform or localized corrosion; except for zinc, which was not resistant in eight-year aged B10.
Carbon Capture and Storage (CCS) is identified as an excellent technology to reach the target of CO2 reduction. However, the safety issue and cost-effectiveness hinder the future of CCS. For the reliability and safety issues of injection wells, the corrosion resistance of the materials used needs to be determined.
In this study, representative low-cost materials including carbon steel 1.8977 and low alloyed steel 1.7225 were investigated in simulated pore water at 333 K and under CO2 saturation condition to represent the worst-case scenario: CO2 diffusion and aquifer fluid penetration. These simulated pore waters were made from relevant cement powder to mimic the realistic casing-cement interface. Electrochemical studies were carried out using the pore water made of cement powder dissolved in water in comparison with those dissolved in synthetic aquifer fluid, to reveal the effect of cement as well as formation water on the steel performance. Two commercially available types of cement were investigated: Dyckerhoff Variodur® and Wollastonite. Variodur® is a cement containing high performance binder with ultra-fine blast furnace slag which can be used to produce high acid resistance concrete. On the other hand, Wollastonite is an emerging natural material mainly made of CaSiO3 which can be hardened by converting to CaCO3 during CO2 injection.
The results showed the pH-reducing effect of CO2 on the simulated pore water/aquifer (from more than 10 to less than 5) leading to the active corrosion process that happened on both 1.8977 and 1.7225. Electrochemical characterization showed negative free corrosion potential and polarisation curves without passive behaviors. The tested coupons suffered from pitting corrosion, which was confirmed by surface analysis. Interestingly, basing on the pit depth measurements from the tested coupons and the hardness of cement powder, it is suggested that Variodur® performed better than Wollastonite in both aspects. The electrochemical data was compared to that resulted from exposure tests to give a recommendation on material selection for bore-hole construction.
Geothermal energy is one of the most promising energy resources to replace fossil fuel. To extract this energy, hot fluids of various salts and gases are pumped up from a geothermal well having a certain depth and location. Geothermal wells in volcanic regions often contain highly corrosive CO2 and H2S gases that can be corrosive to the geothermal power-plants, which are commonly constructed of different steels, such as carbon steel. This research focuses on the corrosion behaviour of carbon steel exposed to an artificial geothermal fluid containing CO2 gas, using an artificial acidic-saline geothermal brine as found in Sibayak, Indonesia. This medium has a pH of 4 and a chloride content of 1,500 mg/L. Exposure tests were conducted for seven days at 70 °C and 150 °C to simulate the operating temperatures for low and medium enthalpy geothermal sources. Surface morphology and cross-section of the specimens from the above experiments were analysed using scanning electron microscope (SEM) and energy dispersive X-ray (EDX). Electrochemical tests via open circuit potential (OCP) and electrochemical impedance spectroscopy (EIS) were performed to understand the corrosion processes of carbon steel in CO2-containing solution both at 70 °C and 150 °C. Localized corrosion was observed to a greater extent at 70 °C due to the less protectiveness of corrosion product layer compared to that at 150 °C, where FeCO3 has a high corrosion resistance. However, a longer exposure test for 28 days revealed the occurrence of localized corrosion with deeper pits compared to the seven-day exposed carbon steel. In addition, corrosion product transformation was observed after 28 days, indicating that more Ca2+ cations incorporate into the FeCO3 structure.
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.
Geothermal energy is an interesting alternative to polluting fossil energy sources. Therefore, in Belgium, two wells have been drilled for a deep geothermal power plant. However, the environment to which the installations are exposed is challenging. The geothermal brine has 165 g/l total dissolved solids (of which 90% are sodium and chlorine) and the production temperature can be up to 130 °C. To assess their suitability to be used in a geothermal power plant, the corrosivity of the artificial brine to three common construction materials was investigated with exposure and electrochemical tests. The metals under consideration are a low-alloyed carbon steel (S235JR), an austenitic stainless steel (UNS S31603) and a duplex stainless steel (UNS S31803). The carbon steel, that was found to corrode uniformly, could be considered as a constructional material if a sufficient wall thickness is chosen. The austenitic stainless steel and the duplex stainless steel demonstrate very low uniform
corrosion rates. They are however susceptible to pitting and crevice corrosion. To guarantee safe operation of the geothermal power plant, the susceptibility of the alloys to stress corrosion cracking should be tested and in situ experiments should be performed.
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.
Interfacial properties related to wettability and corrosion in CO2 transport pipelines are experimentally determined by the sessile and the pendant drop methods. The contact angle of a water drop in a compressed CO2 atmosphere is analyzed on an X70 pipeline carbon steel and compared to that on a martensitic steel S41500 to elucidate the effect of corrosion process on active wetting behaviour. The measurements are performed with liquid CO2 at 278 K and pressures ranging from 5 to 20 MPa. The results show that the contact angle (CA) increases with pressure from 132 ° to 143 ° for S41500 and from 117 ° to 137 ° for X70 and decreases with drop age by 20 ° to 24 ° regardless of the pressure and of the fact that corrosion only occurs on X70, which is confirmed by scanning electron microscopy, element mapping and energy dispersive x-ray spectrometry (EDS) analysis. At higher pressure, the contact angles on both materials converge. Further, related properties like density and interfacial tension were determined. CO2 - saturated water has a higher density than pure water: At 5 MPa saturated water reaches a density of 1017 kg⋅m^(-3) and at 20 MPa 1026 kg⋅m^(-3) compared to pure water with a density of 1002 kg⋅m^(-3) and 1009 kg⋅m^(-3), respectively. In this pressure range the IFT drops from 33 mN⋅m^(-1)at 5 MPa to 23 mN⋅m^(-1) at 20 MPa.
Recent studies have shown that even at a very low concentration of impurities (less than 100 ppmv of SO2, NO2, O2 and H2O) the droplet formation and condensation of sulfuric and nitric acids in dense phase CO2 are possible and observable. To reveal the mechanism of droplet corrosion in dense phase CO2 at high pressure and low temperature, further studies on factors that affect wettability and resulting corrosion behaviors of transport pipeline steels are needed. In this study, effects of surface morphology were investigated by varying surface roughness of carbon steel coupons exposed to CO2 stream containing impurities to measure the wettability by contact angle and to observe the condensation as well as possible droplet corrosion that followed. Other considered factors were: pH of the droplet, temperature, droplet volume, and exposure time.
According to the results of the experiments carried out, the following points can be concluded:
1. Exposure tests showed that specimens with the addition of SiO2 particles and polyaniline particles exhibit better corrosion resistance than specimens with the addition of only polyaniline particles or binder only.
2. Open circuit potential measurements showed that in the beginning of the experiments, both coatings had an open circuit potential 100 mV higher than carbon steel. Within one day of immersion, the potential of carbon steel increased significantly, indicating the formation of oxide layer. After extended exposure the carbon steel potential sat between PS1 (which had higher potential) and PS2 (which had a lower potential) and all three were in the range –600 mV to –500 mV vs Ag/AgCl.
3. Both coatings PS-1 and PS-2 were degraded with increasing exposure time, shown by the decrease of absolute impedance value at low frequency range after 2, 4, and 6 days exposure.
4. Potentiodynamic test was performed after 3 hours and 6 days exposure, and it was shown that the coating in the initial stage exhibited more passive behavior than the specimens exposed for 6 days.
By exposure and electrochemical tests in the laboratory the Cu-effect on corrosion behavior of carbon steel, high-alloyed steels and Ti-alloy can be assessed.
Critical materials specific properties were determined by static exposure and electrochemical tests in an artificial geothermal water with high salinity and low pH, containing Cu. Conclusions were drawn using characteristic potential values.
It could be shown that significant Cu-deposition and -precipitation only occurred in combination with carbon steel. High-alloyed materials (S31603, S31653, S31700, S31703, S31803 and N08904) prevent the disturbing Cu-agglomeration. Therefore, they are suitable to be chosen for future design of the piping system, either in massive or in cladded form, if formation of crevices with non-metallic materials can be excluded.
From the interactions and pitting corrosion point of view, R50400 seems to be most favorable.
According to the results of the experiments carried out, the following points can be concluded:
1. Exposure tests showed that specimens with the addition of SiO2 particles and polyaniline particles exhibit better corrosion resistance than specimens with the addition of only polyaniline particles or binder only.
2. Open circuit potential measurements showed that in the beginning of the experiments, both coatings had an open circuit potential 100 mV higher than carbon steel. Within one day of immersion, the potential of carbon steel increased significantly, indicating the formation of oxide layer. After extended exposure the carbon steel potential sat between PS1 (which had higher potential) and PS2 (which had a lower potential) and all three were in the range –600 mV to –500 mV vs Ag/AgCl.
3. Both coatings PS-1 and PS-2 were degraded with increasing exposure time, shown by the decrease of absolute impedance value at low frequency range after 2, 4, and 6 days exposure.
4. Potentiodynamic test was performed after 3 hours and 6 days exposure, and it was shown that the coating in the initial stage exhibited more passive behavior than the specimens exposed for 6 days.
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.
To study the effects of condensed acid liquid, hereafter referred to as condensate, on the CO2 transport pipeline steels, gas mixtures containing a varying concentration of H2O, O2, NO2, and SO2, were proposed and resulted in the condensate containing H2SO4 and HNO3 with the pH ranging from 0.5 to 2.5. By exposing the pipeline steel to the synthetic condensate with different concentration of acidic components, the corrosion kinetic is significantly changed. Reaction kinetic was studied using electrochemical methods coupled with water analysis and compared with surface analysis (scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray diffractometry (XRD)) of corroded coupons. The results showed that, although the condensation of NO2 in the form of HNO3 causes faster general corrosion rate, it is the condensation of SO2 in the form of H2SO4 or the combination of SO2 and NO2 that may cause much more severe problems in the form of localized and pitting corrosions. The resulting corrosion forms were depended on the chemical nature of acids and their concentration at the same investigated pH. The effects of changing CO2 flow rate and renewing condensate on pitting corrosion were further studied.
Lessons learned from long-term corrosion investigations and –monitoring in saline thermal waters
(2018)
Investigations of corrosion processes in geothermal well in Groß Schönebeck showed
Most tested materials (apart of carbon steel) proved to be corrosion resistant within the installations.
- Stability of coatings cannot be guaranteed.
- Main risk: Electrochemical corrosion of carbon steel casing with dissolved Cu resulting in clogging the reservoir
The corrosion prevention strategy requires use of higher alloyed casing materials depending on resistance parameters, availability and economic feasibility.
Electrochemical deposition of polyaniline on carbon steel for corrosion study in geothermal solution
(2018)
Polyaniline has been widely developed for many applications, e.g., sensor, supercapacitor component, electrochromic devices, and anticorrosion pigments [1]. Although the addition of polyaniline pigment in organic coatings has been an alternative for corrosion protection in industrial application, the protection mechanism is still not fully understood [2]. 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 and tested in geothermal solution to study the contribution of polyaniline in the corrosion protection of a polyaniline-based composite in the geothermal system. The electrochemical deposition was carried out by immersing carbon steel in 0.1 M oxalic acid and 0.05 M aniline, with the polarization potential of -0.6 – 1.5 V vs. Ag/AgCl, and a scan rate of 10 mV/s. To observe the surface/interface reaction between the electrolyte and electrode surface during the electrochemical polymerization, electrochemical impedance spectroscopy (EIS) measurement was applied after each cycle. For corrosion study in the geothermal application, this experiment used an artificial geothermal solution 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. Electrochemical measurements were performed by monitoring the open circuit potential over seven days, with the interruption of EIS every 22 hours. The experiments were performed at room temperature and 150 °C (1 MPa) in a free oxygen environment. Polyaniline coated carbon steel is more durable in a room temperature environment compared to 150 °C, which could be caused by the iron oxalate dissolution at elevated temperature. This degradation was further proven by the impedance spectra, which showed a reduction of approximately ten times for specimens measured at 150 °C as compared to the specimens measured at room temperature.
Nickel-free, nitrogen alloyed austenitic stainless-steels, with about 19 wt.-% Mn and 0,8 wt. % N, are an interesting alternative to classic CrNi austenitic stainless steels due to their superior mechanical properties (Rm > 900 MPa, A5 > 50 %, Av > 350 J) in the solution annealed condition. The formation of chromium-rich nitrides during suboptimal heat treatment, processing or application leads to an inhomogeneous distribution of alloying elements in the microstructure, which reduces the corrosion resistance. Consequently, an accurate knowledge of the sensitization behavior is indispensable for the use of nickel-free, high-nitrogen austenitic stainless steels. The relationship between artificial aging, phase formation and corrosion resistance was investigated on the alloys X8CrMnN18-19 (1.3815) and X8CrMnMoN18-19-2 (1.4456), both alloyed with 0,8 wt.-% Nitrogen, in the present work. The microstructural evolution was studied by LM and SEM while the corrosion resistance was characterized with the electrochemical potentiodynamic reactivation (EPR) and the KorroPad indicator-test. Both alloys showed increased corrosion susceptibility within critical aging parameters. Finally, a sensitization diagram was described successfully for both alloys showing the positive effect of molybdenum.
The copper alloyed stainless steel 1.4542 (X5CrNiCuNb16-4) is used in different areas due to its good mechanical properties and corrosion resistance. Strength and corrosion resistance can be adjusted by the heat treatment, which is of importance for the application of this alloy. The mechanical properties (strength and hardness) are attributed to the dispersive precipitation of the copper rich ε–Phase. The additional precipitation of chromium carbides can reduce the corrosion resistance. Different ageing states were produced to investigate the precipitation behaviour with various methods. Furthermore, the influence of cold-rolling on the precipitation behaviour was studied in comparison to a solution annealed state without deformation. The microstructure was studied by SEM and the variations of hardness and magnetic proportion were characterised. The electrochemical potentiodynamic reactivation (EPR) was used to determine the corrosion resistance and detect chromium depletion in all heat-treated states. The results show that a work hardening accelerates the precipitation rate, while ageing at 600 °C reduces the corrosion resistance due to chromium depletion.
Hardness and pitting corrosion resistance are the major quality criteria of cutlery. Both are achieved by the heat treatment (austenitization, quenching and tempering) of the normally used martensitic stainless steels. The established quality control method regarding the pitting corrosion resistance is an alternating immersion test in 1 % NaCl solution at 60 °C according to DIN EN ISO 8442. This standard test shows a high deviation, which limits any optimization of the heat treatment process. New approaches for corrosion testing of martensitic stainless-steels were developed and used in the last years to connect the weak pitting corrosion resistance of martensitic stainless-steels with the phenomenon of chromium depletion. The tempering temperatures used in the industrial heat treatment of cutlery are too low to explain the appearance of chromium depletion. For this reason, a systematic investigation of three heat treatment parameters (austenitization time, cooling speed and tempering temperature) were performed on the martensitic stainless-steels X50CrMoV15 (1.4116) to detect their contribution to chromium depletion. The electrochemical potentiodynamic reactivation (EPR), which is very sensitive to any change of the microstructure, was used to quantify the degree of chromium depletion. The KorroPad indicator-test was applied to correlate low pitting corrosion resistance to the presence of chromium depletion. The results of all investigations allow conclusions about the very small process window, which is necessary to achieve cutlery with high pitting corrosion resistance.
The KorroPad indicator test was invented at the Federal Institute for Materials Research and Testing to detect stainless-steel surfaces susceptible to pitting corrosion. The KorroPad indicator test is thus an interesting alternative for manufacturers, processors, users and researchers to time consuming exposition experiments and complex electrochemical investigations, which are normally used to reveal surface-related processing errors resulting in reduced pitting corrosion resistance. Furthermore, the KorroPad indicator test can be used to visualize alloy- and microstructure-related factors causing susceptibility to pitting corrosion. The detection limit of the KorroPad indicator test was characterized in this work using reference alloys with different chromium content (5 % to 18 %). The alloy-specific detection limit was shifted successfully to higher chromium content by increasing the concentrations of NaCl and K3[Fe(CN)6]. The modified KorroPads can now be used to establish an alloy-specific quality control regarding the pitting corrosion resistance of different stainless steel grades.
Nickel-free, nitrogen alloyed austenitic stainless-steels, with about 19 wt.-% Mn and 0,8 wt. % N, are an interesting alternative to classic CrNi austenitic stainless steels due to their superior mechanical properties (Rm > 900 MPa, A5 > 50 %, Av > 350 J) in the solution annealed condition. The formation of chromium-rich nitrides during suboptimal heat treatment, processing or application leads to an inhomogeneous distribution of alloying elements in the microstructure, which reduces the corrosion resistance. Consequently, an accurate knowledge of the sensitization behavior is indispensable for the use of nickel-free, high-nitrogen austenitic stainless steels. The relationship between artificial aging, phase formation and corrosion resistance was investigated on the alloys X8CrMnN18-19 (1.3815) and X8CrMnMoN18-19-2 (1.4456), both alloyed with 0,8 wt.-% Nitrogen, in the present work. The microstructural evolution was studied by LM and SEM while the corrosion resistance was characterized with the electrochemical potentiodynamic reactivation (EPR) and the KorroPad indicator-test. Both alloys showed increased corrosion susceptibility within critical aging parameters. Finally, a sensitization diagram was described successfully for both alloys showing the positive effect of molybdenum.
The copper alloyed stainless steel 1.4542 (X5CrNiCuNb16-4) is used in different areas due to its good mechanical properties and corrosion resistance. Strength and corrosion re-sistance can be adjusted by the heat treatment, which is of importance for the application of this alloy. The mechanical properties (strength and hardness) are attributed to the dispersive precipitation of the copper rich ε–Phase. The additional precipitation of chromium carbides can reduce the corrosion resistance. Different ageing states were produced to investigate the precipitation behaviour with various methods. Furthermore, the influence of cold-rolling on the precipitation behaviour was studied in comparison to a solution annealed state without deformation. The microstructure was studied by SEM and the variations of hardness and magnetic proportion were characterised. The electrochemical potentiodynamic reactivation (EPR) was used to determine the corrosion resistance and detect chromium depletion in all heat-treated states. The results show that a work hardening accelerates the precipitation rate, while ageing at 600 °C reduces the corrosion re-sistance due to chromium depletion.
The corrosion resistance of stainless-steels grades is of high importance for the technical safety in different environmental conditions. Processing and surface finish influences the corrosion resistance of ferritic stainless steels, which may be considered for some application in marine environment. Three ferritic stainless steel alloys (X2CrNi12, X2CrTiNb18 and X2CrMoTi18-2) were exposed in four different surface finishes (rolled, dry grinding, glass beaded and electro polished) for five years in marine environment to obtain reliable information about the corrosion resistance. All samples were assessed after 22 and 60 months according to DIN EN ISO 10289 in validation degrees from 1 to 10. Complementary investigation using accelerated chamber test (salt spray test followed by four weeks storage at 30 °C / 80 % relative humidity) and short-term electrochemical methods (electrochemical potentiodynamic reactivation, pitting potentials and the KorroPad method) were conducted to compare their results. The presentation gives an overview on all methods and the generated results, which show benefits and restrictions of long-term, accelerated and short-term corrosion tests.
Hard and wear resistant coatings deposited by PVD techniques have been characterized for decades for their capabilities to protect steel substrates from corrosion. In the present work the effect of Mg incorporated into TiN coatings is described in terms of the corrosion behavior as well as the mechanical and structural properties.
TiN and TiMgN films with Mg contents between 10 and 35 at.% were deposited onto mirror polished 100Cr6 (1.3505) steel samples with 2.5 and 5 μm thickness by using DC magnetron sputtering. The corrosion protection capabilities of the coatings were characterized by neutral salt spray (NSS) test, considering the amounts and sizes of growth defects inherent in each coated sample as determined by a recently developed optical scan method (Large Area High Resolution mapping). The defect data were statistically analyzed for improved interpretation of NSS test results. Chosen growth defects were additionally analyzed by focused ion beam technique. Furthermore the coating composition and morphology, the hardness and the tribological behavior were characterized.
Polished steel samples coated with 2.5 μm TiMgN containing about 35 at.% Mg were in the plane free of corrosion after 24 h in a NSS test. TiMgN with 10 or 20 at.% Mg only provided a slightly improved corrosion protection in relation to pure TiN coatings, which was limited to certain types of growth defects. The highest Mg containing coatings exhibited a decreased hardness down to 1200 or 1800 HV depending on type of deposition (HV 1200: Ti- and Mg-target with rotating substrate holder, 1800: Mg-plugged Ti-target with static substrate holder), but also showed a strongly improved wear resistance against Al2O3 related to pure TiN. By analyzing the NSS test results it was found that the corrosion behavior of the coated samples did not only depend strongly on the Mg content, but also on the sample individual defect concentrations. Therefore this subject is extensively discussed.
Hard coated steel components are used in a wide application range, mostly for protective, wear resistant and decorative purposes. Despite of these coatings being regarded as relatively dense, there is always a high risk of localized corrosion when a coated low alloyed steel component encounters a surrounding high humidity atmosphere or even an aqueous medium. An approach to enhance the corrosion properties is the addition of magnesium to physical vapor deposited hard coatings, like TiN. It has been found that there is a remarkable increase in corrosion resistance in dependence of magnesium content of the TiMgN coating and its surface properties. In this work the authors will explain the underlying corrosion protection mechanisms by means of electrochemical and analytical studies. The positive impact of magnesium in the coating relates on its preferred dissolution vs. steel. This causes the potential to shift to more negative direction with respect to the steel substrate and additionally leads to a temporarily passivation of the steel due to alkalization of the surrounding electrolyte by formation of magnesium hydroxide.
The influence of isothermal ageing on microstructure, sensitisation and pitting corrosion resistance of the lean duplex stainless steel (LDSS) X2CrNiN23-4 was investigated with various electrochemical methods. The aging at 600 °C (from 0.1 h up to 20 h) lead to the formation of precipitations at the ferrite-ferrite (α/α) and ferrite-austenite (α/γ) grain boundaries, inducing sensitisation due to chromium depletion. The degree of sensitisation was evaluated with the double loop electrochemical potentiokinetic reactivation method (DL-EPR) according to ASTM G108 and correlated with critical pitting potentials (Epit) as well as critical pitting temperature (CPT) measured in an electrolyte according to ASTM G48 using electrochemical noise. Up to an ageing time of 1 h, the sensitisation did rise significantly, stabilising at a nearly constant level with a slight drop at 20 h. This behaviour correlated perfectly with the potentiodynamically determined pitting potentials Epit and sensitisation. The CPT showed a higher sensitivity at short ageing times compared to the DL-EPR and Epit. Finally, the KorroPad method was applied to visualise the sensitisation induced reduction of pitting corrosion resistance. The “KorroPad” is an agar-based gel-electrolyte containing 0.1 mol/l sodium chloride (NaCl) and 0.1 mol/l potassium ferricyanide III (K3[Fe(CN)6]), invented at the Federal Institute of Materials Research and Testing in Berlin (Germany) to detect surfaces of stainless steel prone to pitting corrosion. The standard configuration of the KorroPad showed no differentiation for the various aging conditions. Increasing the concentration of both NaCl and potassium ferrocyanide III to 0.5 M shifts the detection limit of the KorroPad method to stainless steels with higher corrosion resistance, producing the same trends detected by standard electrochemical pitting corrosion values (Epit, CPT) and sensitisation (DL-EPR). By that, the KorroPad method was successfully adjusted to the lean-duplex stainless steel X2CrNiN23-4, enabling short-time testing to detect sensitization.
The double loop electrochemical potentiodynamic reactivation (EPR) method is a standardised procedure for detecting and quantifying sensitisation on austenitic, ferritic and ferritic-austenitic stainless-steel grades. This sensitisation is caused by microstructural alternations, as the formation of chromium carbides, nitrides or sigma-phases, which generate local chromium depleted zones nearby. The latter strongly influence the corrosion resistance and the electrochemical response of a stainless steel during electrochemical potentiodynamic reactivation, providing important information on the degree of chromium depletion. In case of martensitic stainless steels, which are used for cutlery and surgical instruments, the heat treatment has a strong impact on the microstructure, the material properties and especially on the corrosion resistance. To study this interaction, the EPR method was modified for the application on martensitic stainless steels with about 13 wt.-% chromium. Different H2SO4 concentrations and EPR-parameters were tested and compared on two standard martensitic stainless-steel grades (AISI 420 A / X20Cr13 and AISI 420 C / X46Cr13) to define applicable parameters. Afterwards, these parameters were used to study the effect of austenitisation time and cooling rate on the corrosion resistance of both martensitic stainless steels. The response of both alloys was different due to the different carbon levels, which will be explained by microstructural investigations in detail. All results allow postulating a process window, in which chromium depletion is suppressed and an optimised corrosion resistance is guaranteed. Based on this research, the modified EPR-test is now used to control the heat treatment and its impact on the corrosion resistance of martensitic stainless steels in the cutlery industry. The EPR-test is thus an interesting alternative for manufacturers, processors, users and researchers to the time-consuming exposition test normally used to characterise the corrosion resistance of martensitic stainless steels.
The copper alloyed stainless steel 1.4542 (X5CrNiCuNb16-4) is used in different areas due to its good mechanical properties and corrosion resistance. Strength and corrosion resistance can be adjusted by the heat treatment, which is of importance for the application of this alloy. The mechanical properties (strength and hardness) are attributed to the dispersive precipitation of the copper rich ε–Phase. The additional precipitation of chromium carbides can reduce the corrosion resistance. Different ageing states were produced to investigate the precipitation behaviour with various methods. Furthermore, the influence of cold-rolling on the precipitation behaviour was studied in comparison to a solution annealed state without deformation. The microstructure was studied by SEM and the variations of hardness and magnetic proportion were characterised. The electrochemical potentiodynamic reactivation
(EPR) was used to determine the corrosion resistance and detect chromium depletion in all heattreated states. The results show that a work hardening accelerates the precipitation rate, while ageing at 600 °C reduces the corrosion resistance due to chromium depletion.
Geothermal brine is a complex system containing a wide variety of dissolved salts resulting from the condition s in a geothermal well. These fluids lead to corrosion in pipes and other parts of geothermal system construction and necessitate intense research efforts in finding new suitable materials. Carbon steel is susceptible to corrosion in geothermal brine especially when it is exposed to a high temperature and high-pressure medium, which is considered to be an aggressive environment. An artificial geothermal water, bas ed on a brine composition found in Indonesia, was used to investigate the performance of high alloyed materials. The electrolyte has pH 4 and contains 1,500 mg/l Cl-, 20 mg/l SO4 2-, 15 mg/l HCO3 -, 200 mg/l Ca 2+, 250 mg/l K+, and 600 mg/l Na+. In order to protect the bare material in geothermal application, it is necessary to either use high alloyed material s or coatings. In this research, a coating system consisting of polyaniline and silicon dioxide was investigated regarding its behavior to protect carbon steel. In detail, the effect of SiO2 and polyaniline (PANi) addition was evaluated by exposure and electrochemical tests for 7 days, i.e. electrochemical impedance spectroscopy (EIS) and open circuit potential (OCP) at room temperature and 150 °C with 1 MPa pressure.
Electrochemical study of polyaniline/silicon dioxide containing coatings in geothermal solution
(2018)
Polyaniline/Silicon Dioxide containing coatings were electrochemically investigated in a saline geothermal solution.
With the increase of exposure time, impedance values of coated specimens decreased at low frequency, which could be caused by the decrease of pore resistance due to electrolyte or water uptake.
Coating system needs further optimization work.
In this work, the focus was set on the corrosion process of condensate as drops on the surface of carbon steels (X52, X70), martensitic steel UNS S41500, and superaustenite UNS N08031 in CO2 atmosphere with impurities at 278 K (to simulate the transportation condition in a buried pipeline). Exposure tests were performed at both normal pressure and high pressure where CO2 is supercritical or in dense phase. The drop, 1 ‑ 10 μL in volume, was prepared by dropping CO2 saturated ultra-pure water onto the surface of steel coupons in a one-liter-autoclave. The CO2 gas stream, simulating the oxyfuel flue gas with varying concentration of impurities (SO2 and O2 ), was then pumped into the autoclave to observe the condensation and corrosion impacts of impurities. Comparable exposure tests were carried out with the same gas mixture and the same volume of water as vapor to observe the drop formation and the corrosion process that follows. The wettability and stability of drops on the surface of steel coupons in CO2 supercritical/dense phase environment was evaluated additionally by contact angle measurement.
Geothermal brine is a complex system containing a wide variety of dissolved salts resulting from the condition s in a geothermal well. These fluids lead to corrosion in pipes and other parts of geothermal system construction and necessitate intense research efforts in finding new suitable materials. Carbon steel is susceptible to corrosion in geothermal brine especially when it is exposed to a high temperature and high-pressure medium, which is considered to be an aggressive environment. An artificial geothermal water, bas ed on a brine composition found in Indonesia, was used to investigate the performance of high alloyed materials. The electrolyte has pH 4 and contains 1,500 mg/l Cl-, 20 mg/l SO4 2-, 15 mg/l HCO3 -, 200 mg/l Ca 2+, 250 mg/l K+, and 600 mg/l Na+. In order to protect the bare material in geothermal application, it is necessary to either use high alloyed material s or coatings. In this research, a coating system consisting of polyaniline and silicon dioxide was investigated regarding its behavior to protect carbon steel. In detail, the effect of SiO2 and polyaniline (PANi) addition was evaluated by exposure and electrochemical tests for 7 days, i.e. electrochemical impedance spectroscopy (EIS) and open circuit potential (OCP ) at room temperature and 150 °C with 1 MPa pressure .