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The presentation summarizes our recent results on the coupled electrochemical methods for high resolution corrosion studies. The combination of Scanning Electrochemical Microscopy (SECM) and multielectrode (MMA) based real-time corrosion monitoring was presented as a new method for achieving high time resolution in local electrochemical analysis. Correlative imaging by means of Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) was demonstrated as a tool for the investigation of local corrosion processes initiated by the intermetallic particles (IMPs) on AA2024-T3 aluminium alloy.
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 and their carbon nanofiller loaded composites on aluminium alloy AA2024-T3 as a model system 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. Atomic force microscopy (AFM) results indicate a very homogeneous and dense film with low surface roughness. Carbon nanofillers were introduced either by mixing into the coating components or in between individual layers to control the separation between the carbon nanofillers and alloy surface. The film chemistry and barrier properties were characterized by means of spectroscopic and electrochemical methods, respectively. The degradation and delamination behavior of the epoxy-based films was characterized by means of in situ AFM corrosion experiments. The quantitative imaging (QI) mode allowed the observation of hydrogen-generation induced blister formation during exposure to corrosive electrolyte and how the local corrosion processes evolved with exposure time. Complementary energy dispersive X-ray spectroscopy (EDX) analysis was performed to correlate the corrosion behavior with the different intermetallic particle chemistries and distributions. The presentation will summarize our results on the effect of interface chemistry and carbon nanofiller – alloy separation on the initiation of local corrosion processes on thin film covered AA2024-T3 aluminium alloys.
In service, most materials are operated under simultaneous corrosive and mechanical load and there are very few methods capable for testing material degradation under these conditions, especially when it comes to high resolution analysis. For this purpose, in this work, a tensile module capable of uniaxial stretching and compression with up to 5 kN force was integrated into an AFM stage. The elimination of the need for sample unmounting and remounting and the resulting possibility of keeping the sample under constant mechanical load during AFM measurements not only enables a precise positioning of the area of interest but also allows for the analysis of processes in the elastic deformation regime.
This methodology was demonstrated for two case studies. Scanning Kelvin Probe Force Microscopy (SKPFM) was used as the main tool to characterize the deformation behavior. Moreover, a flexible electrochemical measurement cell was used to enable electrochemical analysis by means of electrochemical impedance spectroscopy (EIS) and Linear Sweep Voltammetry (LSV) during AFM measurements at different levels of strain. The in situ AFM results are complemented by microstructure analysis by means of electron backscatter diffraction (EBSD).
In the first case study, the deformation induced delamination of a thin organic coating on AA2024 T3 aluminium alloy was investigated as a function of alloy surface treatment. The formation of cracks in the insulating passive film enabled an early detection of deformation processes by means of SKPFM. The second case study focused on the comparison of corrosion and deformation behavior of conventional and additively manufactured 316 stainless steels. In comparison to the conventional 316 stainless steel, the effect of processing was clearly detectable on the additively manufactured material as zones of inhomogeneous potential, which also affected the initiation of local corrosion processes. The contribution will provide detailed information on the new AFM setup and summarize our results from both case studies.
The efficient exploration of novel alloy chemistries is crucial for advancing the development of new materials. Diffusion-controlled synthesis of gradient alloys is an intelligent approach for creating phase diagrams and to effectively identify potential material combinations with tailored properties.
This project focusses on the design of quaternary multi-principle-element alloys (MPEAs) using diffusion couples. Our diffusion system contains an equimolar ternary alloy (FeNiCr) and additional single diffusing elements e.g. Mn and Mo. We determined the optimal temperature ranges for the diffusion thermal treatment by means of ThermoCalc simulations with the aim to form single-phase MPEAs. Microstructure and chemical characterization of the diffusion couples were performed by means of scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). For most alloy couples, the diffusion zone contained a single-phase alloy matrix with diffusion-induced compositional gradient as well as precipitation phases. This heterogeneity makes the diffusion couples interesting materials to investigate local mechanical and corrosion properties. Thus, local corrosion properties were examined using Atomic Force Microscopy (AFM) and Scanning Electrochemical Microscopy (SECM). Nanoindentation was used for the analysis of local mechanical properties.
Based on the results of the local corrosion analysis, we have selected single-phase alloy chemistries along the diffusion zone and reproducibly synthesized these alloys in bulk for detailed corrosion studies by means of potentiodynamic polarization and SECM.
The presentation will briefly summarize our methodology and motivation for using diffusion couples as an efficient tool for exploring phase diagrams of MPEAs in the search for new alloy chemistries and the results of our correlative study on the mechanical and corrosion properties of these materials.
The efficient exploration of novel alloy compositions is crucial for advancing the development of new materials. One widely utilized approach for creating phase diagrams is the use of diffusion-controlled synthesis for gradient alloys. This method is also an effective means for rapidly identifying potential material combinations.
The present study focusses on the exploration of quaternary multi-principle-element alloys (MPEAs) using diffusion multiples. We established a diffusion system by combining an equimolar ternary alloy (FeNiCr) with single diffusing elements Mn and Mo. Using ThermoCalc simulations, we determined suitable temperature ranges where we can expect the formation of single-phase alloys. Depending on the diffusion constants of the selected metals, diffusion times were adjusted to obtain diffusion zones with a depth of greater than 50 μm. Microstructural and compositional information was gathered via scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) and correlated to local mechanical properties evaluated by means of nanoindentation. Local corrosion properties were examined using Atomic Force Microscopy (AFM) and Scanning Electrochemical Microscopy (SECM).
Our results indicate that the ThermoCalc simulations have a good predictive power for crystallographic phases. However, especially with the Mn-FeNiCr system, formation of Cr-rich secondary phases were observed, which led to Cr-depletion and thus to localized corrosion processes in the matrix at the vicinity of the secondary phases. Based on the results of the local electrochemical tests, we have selected single-phase compositions along the diffusion zone and synthesized these alloys in bulk for corrosion studies by means of potentiodynamic polarization and SECM.
The presentation will summarize our methodology using diffusion couples as an
efficient tool for exploring compositional spaces of MPEAs in the search for novel single-phase alloys and the results of our correlative study on the mechanical and corrosion properties of these materials.
Stainless steel AISI 304 surfaces were studied after a mild anodic polarization for oxide growth in the presence and absence of two derivatives of vitamin B2 (riboflavin and flavin mononucleotide) that can be secreted by metal‐reducing bacteria and act as a chelating agent for iron species. The alterations in oxide chemistry were studied by means of surface‐sensitive techniques such as X‐ray photoelectron spectroscopy and time‐of‐flight secondary ion mass spectrometry analysis. The complementary electrochemical characterization revealed a preferential growth of an oxide/hydroxide iron‐rich film that is responsible for an altered pit initiation and nucleation behavior. These findings suggest that as the corrosion behavior is determined by the interplay of the chemical and electronic properties, only a mild anodic polarization in the presence of redox‐active molecules is able to alter the chemical and electronic structure of the passive film formed on stainless steel AISI 304. This helps to achieve a profound understanding of the mechanisms of microbially influenced corrosion (MIC) and especially the possible effects of the redox‐active biomolecules, as they may play an important role in the corrosion susceptibility of stainless steel surfaces.
Metal reducing bacteria (MRB) are capable of utilizing different metals, such as iron, chromium, manganese or uranium as well as many organic compounds, as electron acceptors for their metabolism. Via direct and indirect electron transfer processes MRB are able to convert insoluble passive film species like Fe(III)-oxides to soluble Fe(II)-oxides and hydroxides. This weakening of the passive film not only leads to an acceleration of the general corrosion processes, but also increases the susceptibility of stainless steels to pitting corrosion. Electron transfer mechanisms are not yet fully understood and the role of bacteria in corrosion processes is controversially discussed in the literature. Moreover, recent research indicates that the secretion of electron shuttles like riboflavins by MRB also contributes to the extracellular electron transfer.
This project aims at clarifying the chemical and electrochemical interaction mechanisms of MRB with stainless steel surfaces. To investigate the changes in the oxide chemistry on the stainless steel surface in the presence of biomolecules and MRB a new flow cell has been designed and constructed which enables the collection of XANES (X-ray Absorption Near Edge Structure) spectra in fluorescence mode at the Fe K-edge and electrochemical analysis. Availability of oxygen and the pre-exposure of the MRB to Fe(III) during cultivation have been investigated as parameters with significant effect on the corrosion rates. XANES analysis is supplemented by ex-situ X-Ray Photoelectron Spectroscopy (XPS) and Fourier Transform Infrared Reflection Absorption Spectroscopy (FT-IRRAS) to complete the surface characterisation in terms of the oxide chemistry and the composition of organic residues. Complementary electrochemical quartz crystal microbalance (e-QCM) measurements have been performed to quantify the kinetics of bacterial attachment and biofilm formation. Together with the frequency shift, the evolution of the dissipation signal has been analyzed to investigate the changes in viscosity and structure of the biofilm from initial stages up to maturation. Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) has been used to study the structure and viscoelastic properties of the biofilms after e-QCM experiments.
The presentation will summarize our results on the effects of individual surface and environment related parameters on the chemical/electrochemical interaction mechanisms of MRB leading to passive film degradation on stainless steel surfaces and provide useful insights from a fundamental aspect for the development of novel mitigation strategies for microbiologically influenced corrosion.
The interface of a metal substrate and a biofilm can differ significantly from the surrounding environment. Metal reducing bacteria (MRB), for instance, are capable of utilizing various metallic compounds as electron acceptors. Besides chromium, uranium and manganese as well as many organic compounds, Fe(III) is converted to the soluble form Fe(II) during the bacterial metabolism. This could lead to a weakening of the protective passivation layer on stainless steel and thereby facilitate microbiologically influenced corrosion (MIC). Even tough the processes of electron transfer are not yet entirely explained, the contribution of flavins and other humic substances as electron shuttles is widely discussed in the literature. Moreover, the adsorption of organic thin films on steel surfaces can lead to surface preconditioning and thus to changes in adhesion behavior of bacteria.
The aim of this work is to understand the chemical and electrochemical interaction mechanisms of MRB with steel surfaces by combining electrochemistry and surface-analytical techniques. The investigations primarily focus on the effect of pre-adsorbed thin organic films and self-assembled monolayers (SAMs) on the electron transfer processes between bacteria and steel surfaces. Electrochemical Quartz Crystal Microbalance (eQCM) studies have been performed to investigate the adsorption/desorption kinetics of organic films as well as the formation of biofilms on FeCr electrodes. Furthermore, the evolution of the biofilms on steel surfaces has been analyzed by means of electrochemical impedance spectroscopy (EIS) to support the QCM studies with information on structural changes during different stages of biofilm growth. Electron transfer and corrosion processes have been analyzed by means of square wave voltammetry (SWV) and linear sweep voltammetry (LSV), respectively. The results of electrochemical studies are complemented with microscopic and spectroscopic characterisation of organic adsorbates and analysis of changes in the passive film chemistry and surface morphology.
This presentation will summarize our results on the chemical and electrochemical interaction mechanisms of MRB on steel surfaces leading to passive film degradation. The role of flavins in accelerating corrosion processes will be elucidated in detail to provide useful insights from a fundamental aspect for the understanding of the initial stages of microbiologically influenced corrosion in the presence of MRB.
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.
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.
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.
This work presents the determination of the corrosion characteristics of CrCoNi (medium entropy alloy) and CrMnFeCoNi (high entropy alloy) in 0.1 M NaCl and 0.1 M H2SO4. The morphology and chemical composition of the oxide layers formed on CrCoNi and CrMnFeCoNi were comparatively analyzed by scanning Kelvin probe microscopy (SKPFM) and scanning electron microscopy (SEM) and supported with chemical analysis by means of inductively coupled plasma mass spectrometry (ICP-MS) and X-Ray photoelectron spectroscopy (XPS). The analysis of the 3p core level peaks showed that the oxide layer (native and after anodic passivation) on CrCoNi consisted mainly of Cr oxides, while the oxide layer on CrMnFeCoNi was primarily composed of a mixture of Cr and Fe oxides. In addition, XPS was utilized to assess the oxide layer thicknesses. These results were compared to the thicknesses obtained by means of electrochemical impedance spectroscopy (EIS), with both approaches yielding values up to about 4 nm depending on the electrolyte and the alloy. Cyclic polarization measurements indicated superior corrosion resistance of CrCoNi in both aqueous environments compared to CrMnFeCoNi, as well as to AISI 304 stainless steel.
Multi-principal element alloys (MPEAs) are gaining interest in corrosion and electrocatalysis research due to their electrochemical stability across a broad pH range and the design flexibility they offer. Using the equimolar CrCoNi alloy, we observe significant metal dissolution in a corrosive electrolyte (0.1 M NaCl, pH 2) concurrently with the oxygen evolution reaction (OER) in the transpassive region despite the absence of hysteresis in polarization curves or other obvious corrosion indicators. We present a characterization scheme to delineate the contribution of OER and alloy dissolution, using scanning electrochemical microscopy (SECM) for OER-onset detection, and quantitative chemical analysis with inductively coupled-mass spectrometry (ICP-MS) and ultraviolet visible light (UV-Vis) spectroscopy to elucidate metal dissolution processes. In-situ electrochemical atomic force microscopy (EC-AFM) revealed that the transpassive metal dissolution on CrCoNi is dominated by intergranular corrosion. These results have significant implications for the stability of MPEAs in corrosion systems, emphasizing the necessity of analytically determining metal ions released from MPEA electrodes into the electrolyte when evaluating Faradaic efficiencies of OER catalysts. The release of transition metal ions not only reduces the Faradaic efficiency of electrolyzers but may also cause poisoning and degradation of membranes in electrochemical reactors.
High and medium entropy alloys gained increasing academic and industrial interest as novel materials for engineering applications. This project is aiming to clarify and compare the general and local corrosion properties of high entropy alloy CrMnFeCoNi and medium entropy alloy CrCoNi in different aqueous environments. The focus lies on the local corrosion processes that result either from microstructural imperfections (inclusions, defects at grain boundaries etc.) in the base material or processing related changes in the microstructure and/or local composition.
The corrosion behavior of the alloys was monitored via potentiodynamic polarization experiments and the local corrosion characteristics were further investigated by means of scanning electrochemical microscopy (SECM). Their passivation behavior was analyzed in three different electrolyte systems (NaCl, H2SO4 and NaClO4; c = 0.1M). The characterization of the surface morphology and composition of the passive film was performed by means of atomic force microscopy (AFM), scanning electron microscopy coupled with energy dispersive X-Ray spectroscopy (SEM/EDX) and X-Ray photoelectron spectroscopy (XPS), respectively.
Considering long term corrosion effects, electrochemical work was supported with immersion tests and the analysis of corrosion products by SEM/EDX and XPS depth-profiling. Our results indicate that the medium entropy alloy CrCoNi has a significantly higher corrosion resistance in comparison to the high entropy alloy CrMnFeCoNi. The presentation will summarize some of our results on the mechanistical aspects of the observed high corrosion resistance.
Due to their favorable mechanical and anti-corrosion properties, medium entropy alloys (MEA) are of high academic and industrial interest as novel materials for engineering and catalytic applications. Previous studies on general corrosion behavior indicate high current densities at high anodic potentials for MEAs. Further investigations of the underlying transpassive dissolution and local corrosion behavior remain scarce.
To understand the passivation behavior of MEAs CrCoNi and FeCrNi at high anodic potentials, the mechanisms of transpassive dissolution and the oxygen evolution reaction were investigated in this project. Scanning electrochemical microscopy (SECM) was applied in the interrogative mode for the detection of evolving metal species and oxygen. By means of ICP-MS analysis, dissolved metal species were quantified to provide a fundamental understanding on the transpassive dissolution. As the oxygen evolution reaction (OER) may contribute a large percentile to the observed current at high anodic potentials, SECM measurements were employed to analyze the onset of the OER. Potentiodynamic, potentiostatic and chronoamperometric techniques as well as different electrolytes were used to induce precisely controlled corrosion loads during the SECM experiments and for the ICP-MS analysis. Macroscopic corrosion properties of the alloys, electrical and chemical properties of the passive films were studied by means of potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and X-Ray Photoelectron Spectroscopy (XPS), respectively.
Finally, the analysis of the corrosion morphology and the potential of the surface before, during and after passivity breakdown was carried out by means of in-situ atomic force microscopy (AFM) and scanning Kelvin probe force microscopy (SKPFM). The presentation will summarize our results on the interplay of anodic passivation and oxygen evolution of MEAs in aqueous NaCl electrolytes.
Old materials, new life: Using diffusion-controlled synthesis for discovery of novel alloy systems
(2023)
Multi principal element alloy (MPEAs) concept allows us to rethink how we develop application-tailored, sustainable materials. The vast composition space leads to nearly indefinite material combinations and will facilitate finding Pareto optimal materials with lower CO2 footprint and avoidance of critical minerals as design criteria. To probe this large compositional space efficiently, the use high-throughput screening methods is inevitable. Diffusion-controlled synthesis of gradient materials is the optimal technique for screening complex compositional materials that would otherwise require comprehensive modelling or experimental efforts.
In this study, we have used a series of diffusion couples of pure metals and alloys with the aim to create a materials library with correlated data on composition and microstructure. With future recycling prospects in mind, and possible applications of Cu containing alloys in electrocatalytic carbon dioxide reduction and antimicrobial alloys we have generated diffusion couples of brass (Cu63Zn37) and bronze (Cu89Sn11) with either pure metals (Fe, Ni, etc.) or with binary or ternary alloys (FeNi, FeNiCr etc.). For different diffusion times and temperatures, we calculated diffusion constants for the material combinations. Following a detailed characterisation of the gradient materials, we have investigated general and local corrosion properties, electrocatalytic activity for oxygen evolution reaction (OER) and carbon dioxide reduction reaction (CRR) as well as mechanical properties (hardness, elastic modulus) on single-phase alloys synthesized in bulk by means of vacuum arc-melting based on the selected local compositions.
In most cases, due to the short diffusion times, the contact between the diffusion couples lead to two separate diffusion zones and thus, different alloy families on both sides. Especially with ternary alloys, interesting selective diffusion processes and unexpected repulsion effects were observed. The presentation will provide an overview of the gradient materials with a focus on the functional properties of single-phase alloy families derived from them.