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The performance of functional coatings relies strongly on the stability of the polymer-metal interface. The increasing utilization of multi-material structures in the automotive and aerospace industry necessitates a fundamental understanding of the processes leading to interface degradation for the development of novel strategies to increase corrosion and delamination resistance.
The aim of this project is to investigate the corrosion processes at the buried interface of thin film coated aluminium alloy AA2024-T3 under corrosive and coupled corrosive-mechanical load. A spin coating procedure was developed to synthesize epoxy-like coatings and their nanofiller loaded composites with controlled thickness by layer-by-layer deposition of poly[(o-cresyl glycidyl ether)-co-formaldehyde] and poly-(ethylenimine) bi-layers. Our results indicate that the incorporation of graphene into the epoxy-based coatings leads to the improvement of mechanical and barrier properties. Furthermore, the functional groups play important roles in the interfacial bonding between polymer matrix and the nanofillers. Atomic force microscopy (AFM) results indicate very homogeneous and dense films with a thickness of ~25 nm per bi-layer and the successful integration of the nanofillers into the composite coatings. Ellipsometry measurements of film thickness verified a proportional film growth with the number of deposited layers.
The degradation and delamination behavior of the coating systems was characterized by means of in situ AFM corrosion experiments. Complementary energy dispersive X-ray spectroscopy (EDX) analysis was used to correlate the corrosion and delamination behavior with the different intermetallic particle chemistries and distributions. The presentation will summarize our results on the effect of coating composition and build-up on the local corrosion processes on thin film covered AA2024-T3 aluminium alloys.
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.
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.
This EUROCORR 2021 talk gives current results of the WIPANO research project "safety of prestressing steels." The project targets improving DIN EN ISO 15630-3 according to the reproducibility and scattering of constant load tests to assess the susceptibility of prestressing steels to stress corrosion cracking.
Essential questions which we answered in the talk was: Are test practical on surfaces in delivery condition? What are the hydrogen activities of test solutions A and B during free corrosion and cathodic polarization?
Can the test be improved by a modification of the test cell dimensions?
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.
Corrosion of concrete reinforcement is one of the major damage mechanisms affecting both the load-bearing capacity and the serviceability of reinforced concrete structures significantly. The challenge of detecting corrosion is that the corrosion process in its various forms is not immediately visible, especially in the corrosion initiation phase inside the concrete. When externally discernible damages are observed during visual inspections on the structure, the extent of the damage inside the concrete is often already significant. Corrosion caused by carbonation often leads to severe discoloration of the surface or even large-area spalling of the concrete cover. In contrast, chloride-induced corrosion is usually difficult to observe visually, but can cause much more serious damage in less time. The effect occurs locally and can lead to weakening of the cross-section of the reinforcement. This, in turn, can cause sudden structural collapses without prior notice. Therefore, it is important to investigate whether there is protection against corrosion of the reinforcement in the concrete and to detect active corrosion in the structure at an early stage.
In the meanwhile, various non-destructive and minimally invasive testing methods are available to evaluate the resistance to penetration of corrosion-promoting pollutants and to detect active corrosion. In this paper, a bridge crossing the river Regen (Germany) is used as a case-study to demonstrate how the information obtained applying different testing methods can be combined and evaluated in the context of structural reassessments. Both the results of the permeability testing (Torrent tester) and the electrical resistance measurement (Wenner probe) are considered, as well as active corrosion areas are localized using the half-cell potential mapping combined with the concrete cover measurement with the eddy current method and ground penetrating radar (GPR). The results are evaluated using drill cores and in addition laser-induced breakdown spectroscopy (LIBS) was applied to obtain information about possible ion transport in the concrete.
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.
Investigation of the salinization in marine and offshore environment - test methods and challenges
(2021)
Salinization and contamination of metal surfaces by chloride-containing aerosols is of great importance with regard to corrosion phenomena in the maritime sector and in offshore applications. The evaluation of the scientific literature and regulatory guidelines has shown that there are still many open questions regarding the contamination of metal surfaces by chlorides. This contribution will discuss how salinization of metal surfaces is evaluated and monitored according to current standards and guidelines.
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.
Durch das alkalische Porenwassermilieu wird Stahl im Beton durch Ausbildung einer Deckschicht vor Korrosion geschützt. Unter ungünstigen Umgebungsbedingungen (Karbonatisierung, Chlorideintrag) kann die passive Deckschicht auf der Stahloberfläche zerstört werden. Im weiteren Verlauf können sich durch Volumenexpansion der Korrosionsprodukte korrosionsbedingte Folgeschäden, wie Risse und Abplatzungen am Bauwerk ergeben. Um notwendige Sanierungsmaßnahmen sind frühzeitige und weitgehend zerstörungsfrei ermittelte Informationen über das aktuelle Korrosionsverhalten der Stahlbewehrung von großer Bedeutung. Die Potentialfeldmessung ist ein etabliertes und weit verbreitetes Verfahren zur Beurteilung des Korrosionszustandes der Bewehrung in Stahlbetonbauwerken. Mit Hilfe dieses Verfahrens können Bereiche aktiv korrodierender Bewehrung zerstörungsfrei lokalisiert werden. In der Regel kommt diese Messmethode bei der Detektion chloridinduzierter Korrosion zum Einsatz.
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.
A variety of materials of technological interest change their properties through contact with reactive media. Solid-gas reactions lead to a variety of reaction products on the surfaces and internal interfaces. The observation of nucleation and growth processes in the environment where they occur (in situ) from a chemical-structural perspective is especially challenging for aggressive atmospheres. The talk presents innovative approaches to study corrosion mechanisms using advanced X-ray methods. Using energy dispersive X-ray diffraction and X-ray absorption spectroscopy in different tailor made environmental reaction chambers, valuable insights into high temperature oxidation and sulfidation processes were gained. Fe-based alloys were exposed to hot and reactive atmospheres containing gases like SO2, H2O and O2 at 650°C. During the gas exposure the tailor made reaction chambers were connected to a high energy diffraction end station at the synchrotron. The crystallization and growth of oxide and sulfide reaction products at the alloy surfaces were monitored by collecting full diffraction pattern every minute. Careful examination of shape and intensity of phase-specific reflections enabled to a detailed view on growth kinetics. These studies showed, oxides are the first phases occurring immediately after experimental start. As soon as reactive gas media enter the chamber, the conditions change and different reaction products, such as sulfides start to grow. A comparison of different gas environments applied, illustrated the differences in the type of reaction products. The in situ observation of high temperature material degradation by corrosion made it possible to study the contribution of phases, which are not stable at room temperature. For instance, wuestite (Fe1-xO), was frequently observed at high temperatures in humid gases on Fe with 2 wt.% and 9 wt.% chromium, but not at room temperature. The strength of the occurrence of this phase additionally explains why, despite a higher Cr content, ferritic alloys with 9 wt.% Cr in a challenging atmosphere prevent the intrinsic formation of protective layers. The in situ observations were supplemented by careful considerations of thermodynamic boundary conditions and detailed post characterization by classical metallographic analysis. Additionally, the structure and chemistry of the dominant oxide layers were evaluated using X-ray absorption near edge structure spectroscopy. The talk will give an overview about chances and challenges for studying high temperature corrosion phenomena by advanced X-ray methods.
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.