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MICORRANA II - Development of a hyphenated online-technique for spatially resolved chemical element analysis of micro corrosion processes

English title MICORRANA II - Development of a hyphenated online-technique for spatially resolved chemical element analysis of micro corrosion processes
Applicant Ulrich Andrea
Number 125121
Funding scheme Project funding (Div. I-III)
Research institution Abteilung Analytische Chemie EMPA
Institution of higher education Swiss Federal Laboratories for Materials Science and Technology - EMPA
Main discipline Inorganic Chemistry
Start/End 01.04.2009 - 30.09.2012
Approved amount 243'600.00
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All Disciplines (2)

Discipline
Inorganic Chemistry
Material Sciences

Keywords (9)

analytical chemistry; ultra trace analysis; localized analysis; plasma mass spectrometry; flow injection; electrochemical polarisation; local corrosion mechanisms; local corrosion processes; corrosion

Lay Summary (English)

Lead
Lay summary
Corrosion is an important issue in materials science and engineering. It induces enormous yearly costs of approx. 2 - 5 % of the gross domestic product (GDP). Hence, a detailed understanding of corrosion mechanisms is fundamental for a reliable prediction of corrosion and the development of sustainable materials. The most critical corrosion problems are usually related to localized attack initiating at the weakest points (surface defects, inclusions, grain boundaries, segrega-tions or precipitates). Macroscopic -immersion tests are normally used to achieve elemental information during corrosion dissolution. Within the SNF 200021-109355 Project (MiCorrAna I) a novel analytical set-up was developed, consisting from a micro-flow-capillary, which is coupled via a flow injection system (FI) to an inductively coupled plasma mass spectrometer (ICP-MS). The device enables a preliminary local and time resolved in-situ investigation and an elemental dissolution monitor-ing during corrosion processes at the same time. Within this project, a further capillary minimization is planned as well as the implementation of an additional potentiome-ter control. The new analytical set-up should be applied to investigate corrosion processes e.g. of aluminum alloys with complex inter-metallic phases, amorphous Zr bulk metallic glasses or biodegradable magnesium alloys. The electro-chemical control enables to initiate and control specific corrosion processes (achieved by electrochemical polarization of a metal sample) and simultaneous monitoring of the elemental release by ICP-MS.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Passivation and localised corrosion susceptibility of new Al-Cr-Fe Complex Metallic Alloys (CMAs) in acidic NaCl electrolytes
A. Beni N. Ott E. Ura-Bińczyk M. Rasinski B. Bauer A. Ulrich P. Schmutz (2011), Passivation and localised corrosion susceptibility of new Al-Cr-Fe Complex Metallic Alloys (CMAs) in acidic NaCl electrolytes, in Electrochimica Acta, 56, 10524-10532.
Investigation of corrosion behavior of biodegradable Mg alloys using an online-micro-flow capillary flow injection inductively coupled plasma mass spectrometry setup with electrochemical control
A. Ulrich N. Ott A. Tournier-Fillon N. Homazava P. Schmutz (2011), Investigation of corrosion behavior of biodegradable Mg alloys using an online-micro-flow capillary flow injection inductively coupled plasma mass spectrometry setup with electrochemical control, in Spectrochimica Acta Part B, 66, 536-542.
Passivation of Al–Cr–Fe and Al–Cu–Fe–Cr complex metallic alloys in 1 M H2SO4 and 1 M NaOH solutions
E. Ura-Binczk N. Homazava A. Ulrich R. Hauert M. Levwandowska K.J. Kurzydlowski P. Schmutz (2011), Passivation of Al–Cr–Fe and Al–Cu–Fe–Cr complex metallic alloys in 1 M H2SO4 and 1 M NaOH solutions, in Corrosion Science , 53, 1825-1837.
Online hyphenation of potentiostat to a micro-flow-capillary FI-ICP-MS for simultaneous in situ electrochemical, time and element resolved characterization of local corrosion processes - An applicatio
N. Homazava T. Suter P. Schmutz S. Toggweiler A. Grimberg U. Krähenbühl A. Ulrich, Online hyphenation of potentiostat to a micro-flow-capillary FI-ICP-MS for simultaneous in situ electrochemical, time and element resolved characterization of local corrosion processes - An applicatio, in J. Anal. At. Spectrom, 24, 1161-1169.

Collaboration

Group / person Country
Types of collaboration
Dr. Ngoc-Chang Quach-Vu/EMPA Switzerland (Europe)
- Industry/business/other use-inspired collaboration
A. Grimberg/ETHZ and NASA Switzerland (Europe)
- Industry/business/other use-inspired collaboration
Prof. Dr. Jörg F. Löffler / ETHZ Switzerland (Europe)
- Industry/business/other use-inspired collaboration

Awards

Title Year
Best Poster Presentation award at the European Symposium on Atomic Spectrometry 2010 2012
SCNAT/SCS Chemistry Travel Award 2012 2012
Faculty Award in Chemistry for the best PhD Thesis of the University of Bern, 2010
JAAS Poster Award at 2007 European Plasma Winter Conference 2007
Best Poster Award at PhD Day 2006 2006

Associated projects

Number Title Start Funding scheme
109355 MICORRANA Development of a hyphenated online-technique for spatially resolved chemical element analysis of micro corrosion processes 01.01.2006 Project funding (Div. I-III)
144537 Follow-up-Proposal for the Project MICORRANA II - Development of a hyphenated online-technique for spatially resolved chemical element analysis of micro corrosion processes 01.10.2012 Project funding (Div. I-III)
144537 Follow-up-Proposal for the Project MICORRANA II - Development of a hyphenated online-technique for spatially resolved chemical element analysis of micro corrosion processes 01.10.2012 Project funding (Div. I-III)

Abstract

Summary Background: Corrosion is an important issue in materials science and engineering. It induces enormous yearly costs of approx. 2 - 5 % of the gross domestic product (GDP). In the USA, e.g. the yearly corrosion costs were estimated to about US $300 billion. Hence, a detailed understanding of corrosion mechanisms is fundamental for a reliable prediction of corrosion and the development of sustainable materials. Problem: The most critical corrosion problems are usually related to localized attack initiating at the weakest points e.g. surface defects, inclusions, grain boundaries, segregations or precipitates. Macroscopic -immersion tests are normally used to achieve elemental information during corrosion dissolution. This approach is valid to study uniform corrosion phenomenons, but it is not sufficient to understand the local initiation of corrosion. Furthermore, ex-situ techniques like SEM-EDX (scanning electron microscopy with energy dispersive x-ray - spectroscopy) only provide information before and after a corrosion attack and are limited in lateral and in-depth sensitivity and quantification capabilities. . More surface sensitive methods, like X-Ray Photoelectron (XPS) or Auger (AES) Spectroscopy give much more information on oxidation, passivation and compositional changes related to corrosion processes. But they are clearly focus on the characterization of the solid part of the solid-liquid interface involved in the corrosion process. Electrochemical methods allow local in-situ-investigations with very high sensitivity. Measurement of the current which can be performed down to the femtoampere level with the actual electrochemical systems, gives by far the highest detection limit in terms of corrosion initiation investigation. However, they give only a cumulative parameter, but in certain cases, especially multi-element alloys, information on infinitesimal elemental dissolution during corrosion is necessary. Hence, a method for detailed spatially and time resolved in-situ determination of the dissolution processes is required to investigate in-situ and time resolved the local dissolution mechanisms during corrosion.Project idea and goal of the project: Within the SNF 200021-109355 Project (MiCorrAna I) a novel analytical set-up was developed, consisting from a microflow-capillary, which is coupled via a flow injection system (FI) to an inductively coupled plasma mass spectrometer (ICP-MS). The device enables a preliminary local and time resolved in-situ investigation and an elemental dissolution monitoring during corrosion processes at the same time. The new analytical set-up was already applied to aluminium alloys with complex inter-metallic phases and to amorphous Zr bulk metallic glasses. An additional implementation of a potentiostat for electrochemical control into the novel set-up is planned as a next step. The advantage of the planned electrochemical implementation is an additional possibility to initiate and control specific corrosion processes (achieved by electrochemical polarization of a metal sample) and simultaneous monitoring of the elemental release by ICP-MS.An application of the system for the investigation of aluminium alloys, bulk metallic glasses, and biodegradable alloys for medical applications is planned. The electrochemical implementation should enable the monitoring of elemental release behaviour at different conditions (open circuit potential, at an anodic polarization potential or over the pitting corrosion potential, etc.) Additionally, a further minimization of the flow-capillary diameter is planned. Therefore, a mathematical fluid dynamic model should be established which should enable the assessment of mixing capabilities of different flow-capillary designs. The suitability of the model should be validated by specific tracer experiments. Later-on, the model should become a valuable tool for the optimization of minimized capillary designs. Prospects: The hyphenated technique gains access to important data related to solution chemistry established during local surface degradation processes and corrosion mechanisms. This method, when combined with electrochemical and surface analytical information can become an excellent tool to provide data basis for mechanistic and mathematical modelling of corrosion processes for complex materials. The application of the method is -possible for both complex metallic and non-metallic materials (e.g. glass, polymers, etc.) where corrosion can also occur and in fact represents a problem, too. Risks: Even if the detection power of this hyphaneted technique is extremely high, the dissolution rates of specific passive metals can be extremely low, which could limit the spatial or time resolution capabilities of the method. Moreover, capillary forcesespecially the attraction of the liquid to the wall of the capillary, might limit the minimization of the flowcapilary. However, a recently published study performed within the MiCorrAna I project (without electrochemical initiation), prooved that even highly corrosion resistant amorphous metals can be investigated in certain corrosion media.
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