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GILDES model simulations of the atmospheric corrosion of zinc 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.
2012 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 159, no 3, C123-C128 p.Article in journal (Refereed) Published
Abstract [en]

The GILDES computer based model was successfully applied to the atmospheric corrosion of zinc exposed to low concentrations of carboxylic acids in humidified air at room temperature. Under these exposure conditions the expected precipitated phases are zinc oxide (ZnO), zinc hydroxide (Zn(OH)(2)) and several forms of hydrated zinc carboxylate, Zn(CH3CH2COO)(2) center dot 2H(2)O, Zn(CH3COO)(2) center dot 2H(2)O and Zn(HCOO)(2) center dot 2H(2)O. The results were compared to those from laboratory exposures obtained in the same conditions. The model correctly predicts the trend for ZnO and zinc carboxylate formation found in experimental exposures for the three acids tested. According to the simulations, surface protonation, surface acid base reactions, as well as ligand- and proton-induced dissolution reactions play a major role in the initial atmospheric corrosion of zinc. Henry's law constant (K-H) is found to be an important parameter but uncertain due to different reported literature values. When K-H is increased the formation rate of zinc carboxylate also increases. K-H increases in the sequence propionic acid < acetic acid < formic acid, the same order as found for the calculated dissolution rate.

Place, publisher, year, edition, pages
2012. Vol. 159, no 3, C123-C128 p.
Keyword [en]
GILDES. Zinc, modeling, carboxylic acids, atmospheric corrosion
National Category
Corrosion Engineering
Identifiers
URN: urn:nbn:se:kth:diva-47568DOI: 10.1149/2.072203jesISI: 000299292100042Scopus ID: 2-s2.0-84857406207OAI: oai:DiVA.org:kth-47568DiVA: diva2:455664
Funder
Swedish Research Council
Note
QC 20120326. Updated from submitted to published.Available from: 2011-11-10 Created: 2011-11-10 Last updated: 2017-12-08Bibliographically 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.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2011:54
Keyword
Atmospheric corrosion, copper, zinc, carboxylic acids, modeling, GILDES, in situ, quantification
National Category
Materials Engineering
Identifiers
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)
Opponent
Supervisors
Funder
Swedish Research Council, B 61711
Note
QC 20111114Available from: 2011-11-14 Created: 2011-11-11 Last updated: 2011-11-14Bibliographically approved

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Leygraf, Christofer

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