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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.
The corrosion of steel in reinforced concrete structures is one of the main threats to their durability. Based on the scientific achievements of the past decades the knowledge about the deterioration mechanisms and possible repair strategies for corrosion induced damages have found their way into practice.
It is common sense, that a detailed assessment of the structure is the foundation for a successful repair measure. In addition to the “traditional” singular on-site-procedures such as measurement of concrete cover, carbonation depth, half-cell potentials and chloride contents the monitoring of corrosion related parameters has gained in importance over the past few years.
The advantages of a corrosion monitoring are obvious. In new buildings, structural elements which cannot be assessed after completion (e.g. tunnel segments), or members with electrically isolating coatings can be monitored by means of integrated sensors providing an insight into the development of crucial parameters such as electrochemical potentials, corrosion currents and the electrical resistivity of the concrete. A less known but very beneficial field of application is the use of corrosion monitoring as an integral part of a repair measure based on principles such as the cathodic protection of steel in concrete (CP) or increasing the electrical resistivity of the concrete (IR). By implementing a corrosion monitoring system, it is possible to survey the time dependent effect of the repair measure on the corrosion process which may lead to a confirmation of successful repair measure or to a modification of the repair strategy.
As the principle of cathodic protection for steel in concrete is a recognized repair measure today, the number of applications increases steadily and thus increasing the relevance for corrosion monitoring. Nevertheless, no standards or guidelines concerning the corrosion monitoring are available in Germany today, making it difficult to implement corrosion monitoring in common practice.
With this in mind an international task group formed to develop the specification B12 “Corrosion Monitoring of Reinforced and Prestressed Concrete Structures” published by the German Society for Non-Destructive Testing, DGZfP, spring 2018.
This paper will present the new specification B12 by highlighting the basic measurement principles and illustrating the potentials of corrosion monitoring for new and existing concrete structures by means of case studies.
The corrosion of steel in reinforced concrete structures is one of the main threats to their durability. Based on the scientific achievements of the past decades the knowledge about the deterioration mechanisms and possible repair strategies for corrosion induced damages have found their way into practice.
It is common sense, that a detailed assessment of the structure is the foundation for a successful repair measure. In addition to the “traditional” singular on-site-procedures such as measurement of concrete cover, carbonation depth, half-cell potentials and chloride contents the monitoring of corrosion related parameters has gained in importance over the past few years.
The advantages of a corrosion monitoring are obvious. In new buildings, structural elements which cannot be assessed after completion (e.g. tunnel segments), or members with electrically isolating coatings can be monitored by means of integrated sensors providing an insight into the development of crucial parameters such as electrochemical potentials, corrosion currents and the electrical resistivity of the concrete. A less known but very beneficial field of application is the use of corrosion monitoring as an integral part of a repair measure based on principles such as the cathodic protection of steel in concrete (CP) or increasing the electrical resistivity of the concrete (IR). By implementing a corrosion monitoring system, it is possible to survey the time dependent effect of the repair measure on the corrosion process which may lead to a confirmation of successful repair measure or to a modification of the repair strategy.
As the principle of cathodic protection for steel in concrete is a recognized repair measure today, the number of applications increases steadily and thus increasing the relevance for corrosion monitoring. Nevertheless, no standards or guidelines concerning the corrosion monitoring are available in Germany today, making it difficult to implement corrosion monitoring in common practice.
With this in mind an international task group formed to develop the specification B12 “Corrosion Monitoring of Reinforced and Prestressed Concrete Structures” published by the German Society for Non-Destructive Testing, DGZfP, spring 2018.
This paper will present the new specification B12 by highlighting the basic measurement principles and illustrating the potentials of corrosion monitoring for new and existing concrete structures by means of case studies.
An important aspect with regard to the service life of zinc based galvanic anodes and the durability of the corrosion protection of steel in concrete is the “galvanic chloride extraction”. Chloride ions move in the electric field generated by the current, flowing between the galvanic anode and the cathodic steel. Migration leads to an accumulation of anions, e.g. chloride ions, at the anode and depletion of chlorides near the steel rebar surface. The ion migration was studied on steel reinforced concrete specimens admixed with 3 wt.% chloride/wt. cement and galvanically protected by a surface applied embedded zinc anode (EZA). The zinc anode was embedded and glued to the concrete surface by a geo-polymer based chloride free binder. The EZA was operated over a period of 1 year and the ion distribution between anode (EZA) and cathode (steel reinforcement) was studied by laser induced breakdown spectroscopy (LIBS) after 5 months, 7 months and 12 months. The results show that chloride ions efficiently migrate in the direction of the zinc-anode and accumulate there. Chloride distribution in the EZA correlates with the distribution of zinc ions generated by the anodic dissolution of the zinc anode in the binder matrix. The microstructure of the binder matrix and its interface to the zinc-anode are studied by REM/EDX – preliminary results will be reported.
Electrochemical deposition of polyaniline on carbon steel for corrosion study in geothermal solution
(2019)
Polyaniline has been widely developed for many applications, e.g. sensor, supercapacitor components, electrochromic devices, and anticorrosion pigments. Although the addition of polyaniline pigment in organic coatings has been an alternative for corrosion protection in industrial applications, the protection mechanism is still not fully understood. Herein in this study, as a part of the development of polyaniline/silicon dioxide coating for geothermal application, polyaniline has been deposited electrochemically on carbon steel surface in oxalic acid medium and tested in geothermal solution to understand the contribution of polyaniline to the corrosion protection of a polyaniline-based composite in the geothermal system. To observe the surface/interface reaction between the electrolyte and electrode surface during the electrochemical polymerization, electrochemical impedance spectroscopy (EIS) was applied after each cycle. For corrosion study in the geothermal application, an artificial geothermal solution was used with the composition of 1,500 mg/l Cl⁻, 20 mg/l SO₄²⁻, 15 mg/l HCO₃⁻, 200 mg/l Ca²⁺, 250 mg/l K⁺, and 600 mg/l Na⁺, and pH 4 to simulate a geothermal brine found in Sibayak, Indonesia. An electrochemical measurement was performed by monitoring the open circuit potential over seven days, with the interruption by EIS every 22 hours. The experiments were performed at room temperature and 150 °C (1 MPa) in an oxygen-free environment. Impedance spectra showed a reduction of the total impedance value of approximately 10 times for specimens measured at 150 °C compared to the specimens measured at room temperature, suggesting a less stable layer at high temperature.
The composites combining aluminum and silica nanoparticles with the addition of tetramethylammonium hydroxide (Al-SiO2(T)) and butanol (Al-SiO2(B)) as mixing media have been successfully fabricated. Corrosion behavior of Al-SiO2 composites before and after exposure in 1M NaCl solution was examined using potentiodynamic polarization (Tafel curve analysis). The study was also equipped with scanning electron microscopy (SEM), energy dispersive X-ray (EDX), and X-ray diffraction (XRD) investigations. Before exposure, Al-SiO2(T) exhibited the best corrosion resistance. Performance improvement was indicated by Al-SiO2(B) up to 10 times better than Al-SiO2(T) after exposure. The increased SiO2 content did not significantly enhance the corrosion resistance of the composites. The Al-SiO2 composites with 5% SiO2 content showed very high corrosion resistance (as the optimum composition). Furthermore, pitting corrosion was observed in the Al-SiO2 composites, indicated by the formation of corrosion products at grain boundaries. The product was affected by the presence of SiO2 in the Al matrix and the NaCl environment at 90 °C (approach to synthetic geothermal media: Na+, Cl, H+, OH-). Our study revealed the presence of γ-Al2O3, γ-Al(OH)3, and Al(OH)2Cl as the dominant corrosion products.