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Quantitative in situ analysis of initial atmospheric corrosion of copper induced by carboxylic acids
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
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 [en]
Atmospheric corrosion, carboxylic acids, copper, in situ, IRAS, QCM, coulometric reduction.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-4391ISBN: 978-91-7178-639-5 (print)OAI: oai:DiVA.org:kth-4391DiVA: diva2:12102
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
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

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