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The initial atmospheric corrosion of copper and zinc induced by carboxylic acids: Quantitative in situ analysis and computer simulations
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
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 [en]
Atmospheric corrosion, copper, zinc, carboxylic acids, modeling, GILDES, in situ, quantification
National Category
Materials Engineering
Identifiers
URN: urn:nbn:se:kth:diva-47625ISBN: 978-91-7501-152-3 (print)OAI: oai:DiVA.org:kth-47625DiVA: diva2:455772
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
List of papers
1. Quantitative in situ analysis of initial atmospheric corrosion of copper induced by acetic acid.
Open this publication in new window or tab >>Quantitative in situ analysis of initial atmospheric corrosion of copper induced by acetic acid.
2007 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, 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.

Keyword
reflection-absorption-spectroscopy, potential sweep voltammetry, cathodic reduction, vapor, iron
National Category
Other Basic Medicine
Identifiers
urn:nbn:se:kth:diva-7172 (URN)10.1149/1.2715315 (DOI)000245371700030 ()2-s2.0-34047190810 (Scopus ID)
Note
Uppdaterad från accepted till published(20101105) QC 20101105Available from: 2007-05-22 Created: 2007-05-22 Last updated: 2017-12-14Bibliographically approved
2. Initial atmospheric corrosion of copper induced by carboxylic acids
Open this publication in new window or tab >>Initial atmospheric corrosion of copper induced by carboxylic acids
2007 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 154, no 11, C611-C617 p.Article in journal (Refereed) Published
Abstract [en]

A procedure based on infrared reflection absorption spectroscopy integrated with a quartz crystal microbalance has been developed and used for comparison of initial atmospheric corrosion of copper induced by formic, acetic, and propionic acid. The absolute mass of individual constituents of corrosion products formed, mainly cuprous oxide or cuprite, copper carboxylate, and water or hydroxyl groups, could be obtained under in situ conditions during exposure in 120 ppb of carboxylic acid concentration, 95% relative humidity, 20 degrees C, and up to 96 h of exposure. The quantitative data exhibit consistency between all acids and with postanalysis performed by coulometric reduction. Two spatially separated main pathways have been identified: 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, grows more uniformly over the surface, and 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 their dissociation constants and deposition velocity.

Keyword
Acetic acid, Atmospheric corrosion, Carboxylic acids, Concentration (process), Infrared absorption, Infrared spectroscopy, Quartz crystal microbalances
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-7173 (URN)10.1149/1.2773627 (DOI)000249787900032 ()2-s2.0-34848832714 (Scopus ID)
Note
QC 20100920. Uppdaterad från Submitted till Published (20100920).Available from: 2007-05-22 Created: 2007-05-22 Last updated: 2017-12-14Bibliographically approved
3. Electrochemical reduction modeling of copper oxides obtained during in situ and ex situ conditions in the presence of acetic acid
Open this publication in new window or tab >>Electrochemical reduction modeling of copper oxides obtained during in situ and ex situ conditions in the presence of acetic acid
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
Keyword
potentiodynamic reduction, atmospheric corrosion, copper, acetic acid, copper oxides
National Category
Corrosion Engineering
Identifiers
urn:nbn:se:kth:diva-47542 (URN)10.1016/j.electacta.2009.03.082 (DOI)000266931800013 ()
Note
QC 20111114Available from: 2011-11-10 Created: 2011-11-10 Last updated: 2017-12-08Bibliographically approved
4. GILDES Model Simulations of the Atmospheric Corrosion of Copper Induced by Low Concentrations of Carboxylic Acids
Open this publication in new window or tab >>GILDES Model Simulations of the Atmospheric Corrosion of Copper Induced by Low Concentrations of Carboxylic Acids
2011 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, 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
Keyword
GILDES, modeling, copper, atmospheric corrosion, carboxylic acids
National Category
Corrosion Engineering
Identifiers
urn:nbn:se:kth:diva-47567 (URN)10.1149/2.021112jes (DOI)000297979300052 ()2-s2.0-81355142922 (Scopus ID)
Funder
Swedish Research Council
Note
QC 20111114Available from: 2011-11-10 Created: 2011-11-10 Last updated: 2017-12-08Bibliographically approved
5. GILDES model simulations of the atmospheric corrosion of zinc induced by low concentrations of carboxylic acids
Open this publication in new window or tab >>GILDES model simulations of the atmospheric corrosion of zinc induced by low concentrations of carboxylic acids
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.

Keyword
GILDES. Zinc, modeling, carboxylic acids, atmospheric corrosion
National Category
Corrosion Engineering
Identifiers
urn:nbn:se:kth:diva-47568 (URN)10.1149/2.072203jes (DOI)000299292100042 ()2-s2.0-84857406207 (Scopus ID)
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

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