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GILDES Model Simulations of the Atmospheric Corrosion of Copper Induced by Low Concentrations of Carboxylic Acids
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0002-9453-1333
(Swerea Kimab)
2011 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, Vol. 158, no 12, C429-C438 p.Article in journal (Refereed) Published
Abstract [en]

A computer simulation with a GILDES-based model using the COMSOL multiphysics software was performed for copper exposedto low concentrations of carboxylic acids in humidified air at room temperature. GILDES is a six-regime computer model (Gas,the Interface between gas and liquid, the Liquid, the Deposition layer, the Electrodic region near the surface and the Solid). Thesimulations were compared to previously published in-situ results for copper at the same conditions analysed by a quartz crystalmicrobalance (QCM) and infrared reflection absorption spectroscopy (IRAS). Experimental and calculated results agree with eachother with respect to the effect of corrosion, showing formic acid as the most aggressive followed by acetic and propionic acid.This is supported by a higher ligand- and proton-promoted dissolution found in formic acid exposures, followed by acetic andpropionic exposures. The dominating precipitated phases were Cu2O, Cu(OH)2, Cu(CH3COO)2 · H2O, Cu(HCOO)2 · 4H2O andCu(CH3CH2COO)2 · H2O. Besides Cu2O, the simulations suggest that the hydrated form of the respective carboxylates is the mostlikely compound to be formed in this type of atmospheres.

Place, publisher, year, edition, pages
ECS , 2011. Vol. 158, no 12, C429-C438 p.
Keyword [en]
GILDES, modeling, copper, atmospheric corrosion, carboxylic acids
National Category
Corrosion Engineering
URN: urn:nbn:se:kth:diva-47567DOI: 10.1149/2.021112jesISI: 000297979300052ScopusID: 2-s2.0-81355142922OAI: diva2:455660
Swedish Research Council
QC 20111114Available from: 2011-11-10 Created: 2011-11-10 Last updated: 2012-08-22Bibliographically approved
In thesis
1. The initial atmospheric corrosion of copper and zinc induced by carboxylic acids: Quantitative in situ analysis and computer simulations
Open this publication in new window or tab >>The initial atmospheric corrosion of copper and zinc induced by carboxylic acids: Quantitative in situ analysis and computer simulations
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Degradation of metals through atmospheric corrosion is a most important and costly phenomenon with significant effects on, e.g., the lifespan of industrial materials, the reliability of electronic components and military equipment, and the aesthetic appearance of our cultural heritage. Atmospheric corrosion is the result of the interaction between the metal and its atmospheric environment, and occurs in the presence of a thin aqueous adlayer. The common incorporation of pollutant species into this adlayer usually enhances the degradation process. During atmospheric corrosion indoors, low concentrations of organic atmospheric constituents, such as formic, acetic, propionic, butyric and oxalic acids, have found to play an accelerating role on a broad range of metals or their alloys, including lead, steel, nickel, copper, cadmium, magnesium and zinc.

In this doctoral thesis the initial stages of the atmospheric corrosion of copper exposed to synthetic air, aiming at simulating representative indoor atmospheric environments, have been investigated both experimentally and through a computational method. The experiments have been based on a unique analytical setup in which a quartz crystal microbalance (QCM) was integrated with infrared reflection absorption spectroscopy (IRAS). This enabled the initial atmospheric corrosion of copper to be analyzed during ongoing corrosion in humidified air at room temperature and additions of 120 ppb (parts per volume billions) of acetic, formic or propionic acid. The main phases identified were copper (I) oxide (Cu2O) and various forms of copper carboxylate, and their amounts deduced with the different analytical techniques agree with a relative accuracy of 12% or better.

Particular emphasis has been on the identification of different forms of copper (I) oxide generated during these exposures. An electrochemically based model has been proposed to describe how copper oxides, formed in the presence of acetic acid, are electrochemically reduced in neutral solution. The model includes the electrochemical reduction of copper (II) oxide (CuO), amorphous copper (I) oxide (Cu2O)am, intermediate copper (I) oxide (Cu2O)in, and crystalline copper (I) oxide (Cu2O)cr. A good agreement is obtained between the model and experimental data, which supports the idea of a reduction sequence which starts with copper (II) oxide and continues with the reduction of the three copper (I) oxides at more negative potentials.

The quantified analytical data obtained in this doctoral study on corrosion products formed on copper, and corresponding data on zinc reported elsewhere, were used as the starting point to develop a computational model, GILDES, that describes the atmospheric corrosion processes involved. GILDES considers the whole interfacial regime in which all known chemical reactions have been considered which are assumed to govern the initial atmospheric corrosion of copper or zinc in the presence of carboxylic acids. The model includes two separate pathways, a proton-induced dissolution of cuprous ions or zinc ions followed by the formation of either copper (I) oxide or zinc (II) oxide, and a carboxylate-induced dissolution followed by the formation of either copper (II) carboxylate or zinc (II) carboxylate. The model succeeds to predict the two main phases in the corrosion products and a correct ranking of aggressiveness of the three acids for both copper and zinc. The ranking has been attributed to differences in acid dissociation constant and deposition velocity of the carboxylic acids investigated.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2011. ix, 65 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2011:54
Atmospheric corrosion, copper, zinc, carboxylic acids, modeling, GILDES, in situ, quantification
National Category
Materials Engineering
urn:nbn:se:kth:diva-47625 (URN)978-91-7501-152-3 (ISBN)
Public defence
2011-12-02, F3, Lindstedtsvägen 26, KTH, Stockholm, 13:00 (English)
Swedish Research Council, B 61711
QC 20111114Available from: 2011-11-14 Created: 2011-11-11 Last updated: 2011-11-14Bibliographically approved

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