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The performance of functional coatings and adhesively joined hybrid components relies strongly on the stability of the polymer-metal interface. With the increasing utilization of multi-material structures in the automotive and aerospace industry, it is of great scientific and technical interest to understand the processes leading to interface degradation and to develop novel strategies to increase corrosion and delamination resistance.
The aim of this project is to develop thin epoxy-based films on aluminium alloy AA2024-T3 as a model system and to investigate their interfacial stability under corrosive and coupled corrosive-mechanical load. Electrochemical and spectroscopic methods were used for the characterisation of the film properties and in situ corrosion experiments were performed by means of AFM. The deformation properties of the aluminium alloy and the model coatings were investigated by means of scanning Kelvin probe force microscopy (SKPFM) utilizing the integrated tensile stage.
The presentation will give a brief overview of the capabilities of the new AFM setup to foster future collaborations and summarize our work on the interface stability of model coatings.
Ferritic high temperature alloys are widely used as boiler tube and heat exchanger materials in coal, biomass and co-fired power plants. All technologies have in common that the applied materials are exposed to different temperatures, process pressures and reactive atmospheres that lead to a change of the material properties and a further degradation of the material. Material changes caused by aging in highly corrosive and toxic gases such as SO2 are mainly studied ex situ after the reaction is finished. The solid material is deposited in the atmosphere for a certain period of time, and material changes are then examined by various microscopic techniques such as optical microscopy (OM), electron microprobe analysis (EMPA), scanning electron microscopy (SEM and TEM) and X-ray diffraction (XRD). Nevertheless, extensive efforts were made to study material changes of high temperature alloys under oxidizing and reducing atmospheres by environmental scanning electron microscopy or in situ TEM techniques However, the possibilities of microscopic in situ techniques are very limited for the use of highly corrosive and toxic gases such as SO2. Since Sulfur induced corrosion at temperatures relevant for coal and biomass fired power plants, which is causing breakaway oxidation and sulfide precipitation at grain boundaries, is still of scientific interest, the current work focuses on the effect of SO2 in an initial stage of corrosion of ferritic alloys. For the analysis of early stages of combined oxidation and sulphidation processes of Fe-Cr model alloys the usage of a light furnace to conduct a rapid reactive annealing experiment is feasible. Previous studies presented distinct results of the influence of chromium on early high temperature corrosion by SO2 by this technique and subsequent classical metallographic analyses. However, it is still not possible to trace the corrosion mechanism in real time by conducting single aging experiments. The current work introduces two different approaches to study the initial stages of high temperature oxidation processes by applying above state of the art X-ray diffraction and spectroscopy methods. One part focuses on the real time observation of the formation of corrosion products such as oxides and sulfides by energy dispersive X-ray diffraction (EDXRD). The potential of this technique to study crystallization and growth processes of thin films in a reactive environment in real time was previously shown for different compound semiconductors. This approach was now applied to follow oxidation and sulphidation processes of ferritic model alloys in SO2 and SO2/H2O environments. The diffraction signals of the X-rays were detected during the corrosion process and the peak area and positions were analyzed as a function of time. This procedure enables monitoring external oxide growth and material loss in real time in an early stage of corrosion.
The other part of the current work presents the possibilities of X-ray absorption near edge structure spectroscopy (XANES) to characterize oxide scales and their growth mechanisms. Precise phase identification and quantification of corrosion products in a multi-phase oxide/sulfide scale is a pre-requisite to understand diffusion paths of metal ions and gas components. It is a challenging task to distinguish structurally similar reaction products such as Fe3O4 and FeCr2O4 especially in thin films with texture effects by diffraction. To illustrate for example Cr-out diffusion of an alloy throughout an inner and external oxide scale the differentiation of Fe3O4 and FeCr2O4 is indispensable. XANES uses the photoionization effect at the metal absorption edge in an aging product and accesses by this structural and chemical information. The current work uses XANES at the Fe-K and Cr-K absorption edge to identify various aging products grown as thin layers on alloys after short time aging experiments. A reaction chamber for combining high temperature oxidation experiments with surface sensitive X-ray absorption near edge structure spectroscopy will be introduced and first results of XANES on scales at high temperatures will be presented.
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.
The performance of adhesively joined hybrid components relies strongly on the stability of the adhesive-material interface. With the increasing utilization of multi-material structures in the automotive and aerospace industry, it is of great scientific and technical interest to understand the processes leading to adhesive failure and to develop novel strategies to increase corrosion and delamination resistance of adhesive joints.
The aim of this study is to develop thin epoxy based films and their carbon nanofiller loaded composites on aluminium alloy AA2024-T3 and to investigate their interfacial stability under corrosive and coupled corrosive-mechanical load. Spin coating was used for the layer-by-layer deposition of poly[(o-cresyl glycidyl ether)-co-formaldehyde] and poly-(ethylenimine) bi-layers. Carbon nanofillers are introduced either by mixing into the coating components or in between individual layers. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) analysis was performed to investigate the porosity and water uptake of the model films, respectively. Atomic force microscopy (AFM) results indicated a very homogeneous and dense film with low surface roughness. The bi-layer thickness ranged between 30 to 40 nm. Electrochemical measurements show a higher corrosion resistance with the increase of the bi-layer number.
The main novelty of this contribution is the in-situ AFM investigations under coupled corrosive-mechanical load. For this purpose, a tensile module capable of uniaxial stretching and compression with up to 5 kN force was integrated into the AFM stage. Stretching experiments were performed to investigate the mechanical properties and adhesion of the films, as well as structural changes of the film morphology during uniaxial deformation. The contribution will provide detailed information on the new AFM setup and summarize our results on the stability of model epoxy and nanocomposite films on AA2024-T3.
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.
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.
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.
We investigated the effect of water vapor in the initial stages of SO2 corrosion of an Fe-9Cr-0.5Mn model alloy at 650 °C. Two separate experiments were run, one with 99.5%-Ar + 0.5%-SO2 and one with 69.5%-Ar + 0.5%-SO2 with 30%-H2O atmosphere. During the experiment the scale growth was observed in-situ, using energy dispersive X-ray diffraction (EDXRD). Our results confirm an increased speed of oxygen transport into the material, with the addition of water, while the transport of sulfur appears to be less affected.
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.