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Corrosion inhibition of copper with octadecylphosphonic acid (ODPA) in a simulated indoor atmospheric environment
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0002-9417-9579
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0002-2510-7766
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0002-9453-1333
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0002-8537-0881
2021 (English)In: Corrosion Science, ISSN 0010-938X, E-ISSN 1879-0496, Vol. 192, no 109777Article in journal (Refereed) Published
Abstract [en]

The corrosion inhibition of self-assembled octadecylphosphonic acid (ODPA) layers on non-oxidized and pre-oxidized copper and Langmuir-Blodgett deposited ODPA layers on pre-oxidized copper was investigated under a simulated indoor atmospheric corrosion environment containing 80% RH and 100 ppb formic acid. The corrosion process was monitored in-situ with infrared absorption/reflection spectroscopy, and the corrosion products were further characterised by grazing incidence X-ray diffraction. Nano-FTIR microscopy was used to reveal the nature, size, and distribution of the corrosion products on the nanoscale. The combination of pre-formed cuprite and ODPA layers, both with only some nanometres thickness, provided an excellent protection under this environment.

Place, publisher, year, edition, pages
Elsevier BV , 2021. Vol. 192, no 109777
National Category
Surface- and Corrosion Engineering
Identifiers
URN: urn:nbn:se:kth:diva-302660DOI: 10.1016/j.corsci.2021.109777ISI: 000700924900002Scopus ID: 2-s2.0-85113958426OAI: oai:DiVA.org:kth-302660DiVA, id: diva2:1598397
Note

QC 20211011

Available from: 2021-09-28 Created: 2021-09-28 Last updated: 2025-02-09Bibliographically approved
In thesis
1. Nanoscale studies of the atmospheric corrosion of copper protected by ultrathin organic films
Open this publication in new window or tab >>Nanoscale studies of the atmospheric corrosion of copper protected by ultrathin organic films
2021 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Copper (Cu) has been utilised by humans for millenniums and has become an indispensable metal in modern industry and in our infrastructure. However, corrosion, as a natural process for metallic materials, takes place on copper surfaces in most environments. Thus, understanding corrosion and corrosion protection of copper is of utmost importance to maintain its performance and prolong the lifetime of the applications. Corrosion has been revealed to start from local weak areas of the copper surface. However, the corrosion initiation and propagation mechanism on copper on a molecular level are far from clear.

In this thesis, the corrosion initiation of copper under a simulated indoor atmosphere where formic acid and humidity are present was studied. The corrosion process was monitored in-situ, and the formed corrosion products were characterised on the macro-, micro-, and nanoscale by various analytical techniques from both horizontal and vertical directions of the corroded surfaces. The localised dissolution and formation of the Cu2O layer on narrowly separated areas on the nanoscale were observed both microscopically and spectroscopically. A novel technique, nano infrared spectroscopy (nano-FTIR), was used to probe the formed corrosion products on the nanoscale. Due to the novelty of nano-FTIR, only a few studies in corrosion science using this technique were reported. Thus, this thesis also shows the capability of employing nano-FTIR in corrosion studies.

The ability of ultrathin organic films to protect copper under indoor atmospheres was also studied in this thesis. The main focus was on octadecylphosphonic acid (ODPA), for which the self-assembly process was examined in detail. A multilayer formation of ODPA on copper was observed under the self-assembly deposition, and the thickness of ODPA films increased with the deposition time. The reason for forming multilayers was attributed to the Cu+ ion release during the deposition, resulting in the formation of a Cu+-ODPA complex. The protective ability of these self-assembled ODPA films as well as Langmuir-Blodgett (LB)-deposited films on non-oxidised and pre-oxidised copper was examined under the same exposure conditions as for the unprotected copper. A remarkable ability to protect the surface was observed for the self-assembled and LB-deposited ODPA films on pre-oxidised copper.

Abstract [sv]

Koppar har använts av människor i tusentals år och är numera en ovärderlig metall iden moderna industrin och i många samhällsfunktioner. Korrosion, som är en naturlig process för metaller, är dock något som påverkar koppar i de flesta miljöer, varvid dess egenskaper kan försämras. Det är därför av yttersta vikt att i detalj förstå hur koppar korroderar och även hur koppar kan skyddas för att säkerställa dess funktion och för att förlänga livslängden i applikationer där koppar används. Det är känt att korrosion börjar lokalt i svaga punkter på ytan, men hur korrosionen initieras och fortgår är långt ifrån klart på nanonivå.

I denna avhandling har korrosion av koppar som utsatts för en simulerad inomhusmiljö bestående av fuktig luft och myrsyra studerats. Korrosionsprocessen studerades in-situ och korrosionsprodukterna undersöktes med ett flertal olika analytiska instrument på flera nivåer, från makro-, via mikro-, till nanoskopisk nivå och både i horisontell och vertikal riktning. Såväl den lokala upplösningen som skapandet av lager av Cu2O i smala separerade områden studerades på nanonivå med både mikroskopi och spektroskopi. Den nya tekniken ”Nano-FTIR”, som bara har använts i ett fåtal korrosionsstudier tidigare, användes för att studera korrosionsprodukterna på nanonivå. Ett mål med avhandlingen var därför att visa möjligheterna med denna teknik för korrosionsstudier.

Förmågan hos ultratunna organiska filmer att skydda koppar mot inomhuskorrosion studerades i denna avhandling. Huvudfokus låg på oktadecylfosfonsyra (ODPA), för vilken självassocieringsprocessen även studerades i detalj. Under självassocieringsprocessen på kopparytan skapades ett multilager, vars tjocklek ökade med deponeringstiden. Bildandet av detta multilager förklarades genom en mekanismdär Cu+joner frisattes och bildade komplexet Cu+ - ODPA. Förmågan att skydda ickeoxiderade och föroxiderade kopparytor från korrosion under samma betingelser som den oskyddade kopparn undersöktes för dessa självassocierade filmer och även för ODPA-filmer deponerade med Langmuir-Blodgett (LB)-tekniken. Både de självassocierade filmerna och LB-filmerna på föroxiderad koppar uppvisade en enastående förmåga att förhindra korrosionen.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2021. p. 64
Series
TRITA-CBH-FOU ; 2021:38
Keywords
Atmospheric corrosion, copper, corrosion inhibition, Langmuir-Blodgett (LB) deposition, self-assembly deposition, nano-FTIR, octadecylphosphonic acid (ODPA).
National Category
Surface- and Corrosion Engineering
Research subject
Chemistry
Identifiers
urn:nbn:se:kth:diva-302664 (URN)978-91-8040-004-6 (ISBN)
Public defence
2021-10-29, Kollegiesalen, Brinellvägen 8, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 2021-10-04

Available from: 2021-10-04 Created: 2021-09-28 Last updated: 2025-02-09Bibliographically approved

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Publisher's full textScopushttps://doi.org/10.1016/j.corsci.2021.109777

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Zhao, WeijieChang, TingruLeygraf, ChristopherJohnson, C. Magnus

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