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Quantitative in situ analysis of initial atmospheric corrosion of copper induced by acetic acid.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Corrosion Science.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Corrosion Science.ORCID iD: 0000-0002-9453-1333
2007 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, Vol. 154, no 5, 272-278 p.Article in journal (Refereed) Published
Abstract [en]

The initial atmospheric corrosion of copper was investigated by means of a quantitative in situ analysis in an atmospherecontaining 120 ppb of acetic acid and 95% relative humidity using a quartz crystal microbalance (QCM) integrated with infraredreflection absorption spectroscopy (IRAS). Crystalline cuprous oxide (various structural forms of Cu2O) and hydrated copperacetate were detected as corrosion products during up to 100 h of exposure. The quantification of data was made possible throughan observed linear relationship between the absorbance of vibrations (IRAS)of both phases and the corresponding mass (QCM).The quantification of cuprous oxide was further supported by ex situ coulometric reduction of the corrosion products. The growthrate of cuprous oxide was initially very fast but almost zero after 20 h exposure where it reached an average thickness of13 ± 1 nm. Copper acetate exhibited a more constant growth rate. Atomic force microscopy showed a uniform growth of cuprousoxide with surface roughness that increased with time and localized formation of copper acetate. The quantified data are consistentwith a previously proposed model that involves proton- and acetate-induced dissolution of copper and subsequent precipitation ofcuprous oxide and copper acetate.

Place, publisher, year, edition, pages
2007. Vol. 154, no 5, 272-278 p.
Keyword [en]
reflection-absorption-spectroscopy, potential sweep voltammetry, cathodic reduction, vapor, iron
National Category
Other Basic Medicine
Identifiers
URN: urn:nbn:se:kth:diva-7172DOI: 10.1149/1.2715315ISI: 000245371700030Scopus ID: 2-s2.0-34047190810OAI: oai:DiVA.org:kth-7172DiVA: diva2:12100
Note
Uppdaterad från accepted till published(20101105) QC 20101105Available from: 2007-05-22 Created: 2007-05-22 Last updated: 2011-11-14Bibliographically approved
In thesis
1. Quantitative in situ analysis of initial atmospheric corrosion of copper induced by carboxylic acids
Open this publication in new window or tab >>Quantitative in situ analysis of initial atmospheric corrosion of copper induced by carboxylic acids
2007 (English)Licentiate thesis, comprehensive summary (Other scientific)
Abstract [en]

The interaction of carboxylic acids with copper is a phenomenon found both outdoors and, more commonly, indoors. The influence on copper of some carboxylic acids (formic, acetic, propionic, and butyric) have so far been studied at concentrations levels at least three or four orders of magnitude higher than actual indoor conditions (< 20 ppb, volume parts per billion), and with only limited emphasis on any mechanistic approach. In this licentiate study a unique analytical setup has been successfully applied for in situ characterization and quantification of corrosion products formed during initial atmospheric corrosion of copper in the presence of acetic, formic or propionic acid. The setup is based on monitoring mass changes by the quartz crystal microbalance (QCM) and simultaneously identifying the chemical species by infrared reflection-absorption spectroscopy (IRAS). Post-analysis of corrosion products was performed by coulometric reduction (mass of copper (I) oxide formed), grazing incidence x-ray diffraction (phase identification) and atomic force microscopy (surface topography).

The absolute amounts of mass of individual constituents in the corrosion products, mainly copper (I) oxide or cuprite, copper (II) carboxylate and water or hydroxyl groups, have been deduced in situ during exposure in 120 ppb of carboxylic acid concentration, 95% relative humidity and 20ºC. An overall result is the consistency of analytical information obtained. For copper (I) oxide the quantified data estimated from IRAS, QCM or coulomeric reduction agrees with a relative accuracy of 12 % or better.

The interaction of copper with the carboxylic acids seems to follow two spatially separated main pathways. A proton-induced dissolution of cuprous ions followed by the formation of copper (I) oxide, and a carboxylate-induced dissolution followed by the formation of copper (II) carboxylate. The first pathway is initially very fast but levels off with a more uniform growth over the surface. This pathway dominates in acetic acid. The second pathway exhibits a more constant growth rate and localized growth, and dominates in formic acid. Propionic acid exhibits low rates for both pathways. The difference between the carboxylic acids with respect to both total corrosion rate and carboxylate-induced dissolution can be attributed to differences in acid dissociation constant and deposition velocity.

Place, publisher, year, edition, pages
Stockholm: Kemi, 2007
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2007:21
Keyword
Atmospheric corrosion, carboxylic acids, copper, in situ, IRAS, QCM, coulometric reduction.
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-4391 (URN)978-91-7178-639-5 (ISBN)
Presentation
2007-05-22, Sal V1, KTH, Teknikringen 76, 1tr, Stockholm, 10:00
Opponent
Supervisors
Available from: 2007-05-22 Created: 2007-05-22 Last updated: 2012-03-20
2. 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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