Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Electrochemical reduction modeling of copper oxides obtained during in situ and ex situ conditions in the presence of acetic acid
Department of Materials, University of Antioquia. (Corrosion and Protection Group)
Department of Materials, University of Antioquia. (Corrosion and Protection Group)
Department of Materials, University of Antioquia. (Corrosion and Protection Group)
2009 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 54, no 20, 4676-4681 p.Article in journal (Refereed) Published
Abstract [en]

We used the potentiodynamic reduction technique to study the mechanism of copper oxide formation inthe presence of acetic acid.We performed all reductions under neutral conditions (0.1MKCl) until hydrogenevolution. We produced the copper oxides in an environment containing 0, 500, and 800 ppb aceticacid at high relative humidity. We then compared experimental results between electrochemically producedoxide films obtained by imposing anodic potentials to copper specimens in several concentrationsof pure acetic acid (1, 0.1, 0.01 and 0.001 M). We found that, as the concentration of the acid decreases,the formation of the copper oxide (I) increases.We also found the same peaks in samples produced underthe synthetic environment.We modeled the curves, taking into account the electrochemical reduction ofcopper (II) oxide (CuO), amorphous cuprite (Cu2O)am, intermediate cuprite (Cu2O)in, crystalline cuprite(Cu2O)cr, and hydrogen. These oxides have been previously detected in similar conditions. We found noevidence of copper carboxylate founding samples produced by the electrochemical method.

Place, publisher, year, edition, pages
Elsevier , 2009. Vol. 54, no 20, 4676-4681 p.
Keyword [en]
potentiodynamic reduction, atmospheric corrosion, copper, acetic acid, copper oxides
National Category
Corrosion Engineering
Identifiers
URN: urn:nbn:se:kth:diva-47542DOI: 10.1016/j.electacta.2009.03.082ISI: 000266931800013OAI: oai:DiVA.org:kth-47542DiVA: diva2:455658
Note
QC 20111114Available 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

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Gil, Harveth
In the same journal
Electrochimica Acta
Corrosion Engineering

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 126 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf