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The nature of self-assembled octadecylphosphonic acid (ODPA) layers on copper substrates
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 (SCI), Applied Physics, Materials and Nanophysics.ORCID iD: 0000-0002-6785-8293
Institute of Particle Technology (LFG), Friedrich-Alexander-Universität-Erlangen-Nürnberg (FAU), 91058 Erlangen, Germany.
Department of Chemistry Ångström Laboratory, Division of Physical Chemistry, Uppsala University, SE-751 20 Uppsala, Sw.
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2021 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 581, p. 816-825Article in journal (Refereed) Published
Abstract [en]

Hypothesis: The self-assembly of amphiphilic molecules onto solid substrates can result both in the formation of monolayers and multilayers. However, on oxidized and non-oxidized copper (Cu), only monolayer formation was reported for phosphonic acids possessing one phosphate head group. Here, the adsorption of octadecylphosphonic acid (ODPA) on Cu substrates through a self-assembly process was investigated with the initial hypothesis of monolayer formation. Experiments: The relative amount of ODPA adsorbed on a Cu substrate was determined by infrared reflection/absorption spectroscopy (IRRAS) and by atomic force microscopy (AFM) investigations before and after ODPA deposition. X-ray photoelectron spectroscopy (XPS) with sputtering was used to characterize the nature of the layers. Findings: The results show that the thickness of the ODPA layer increased with deposition time, and after 1 h a multilayer film with a thickness of some tens of nm was formed. The film was robust and required long-time sonication for removal. The origin of the film robustness was attributed to the release of Cu ions, resulting in the formation of Cu-ODPA complexes with Cu ions in the form of Cu(I). Preadsorbing a monolayer of octadecylthiol (ODT) onto the Cu resulted in no ODPA adsorption, since the release of Cu(I) ions was abolished.

Place, publisher, year, edition, pages
Academic Press Inc. , 2021. Vol. 581, p. 816-825
Keywords [en]
Atomic force microscopy, Copper leaching, Infrared reflection/absorption spectroscopy, Octadecylphosphonic acid, Self-assembled monolayers, X-ray photoelectron spectroscopy, Copper metallography, Deposition, Heavy ions, Monolayers, Multilayer films, Multilayers, Substrates, X ray photoelectron spectroscopy, Amphiphilic molecules, Copper substrates, Infrared reflections, Initial hypothesis, Monolayer formation, Octadecylphosphonic acids, Phosphonic acids, Self assembly process, Copper compounds, copper ion, octadecylthiol, phosphonic acid derivative, self assembled monolayer, thiol derivative, unclassified drug, absorption spectroscopy, acid deposition, adsorption, analytic method, Article, chemical analysis, chemical structure, cheminformatics, complex formation, controlled study, film thickness, infrared spectroscopy, priority journal, reflectometry, ultrasound, X ray photoemission spectroscopy
National Category
Condensed Matter Physics Materials Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-285301DOI: 10.1016/j.jcis.2020.07.058ISI: 000604318400020PubMedID: 32818682Scopus ID: 2-s2.0-85089435386OAI: oai:DiVA.org:kth-285301DiVA, id: diva2:1506170
Note

QC 20201202

Available from: 2020-12-02 Created: 2020-12-02 Last updated: 2024-01-10Bibliographically 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)
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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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Zhao, WeijieGöthelid, MatsLi, GenLeygraf, ChristopherJohnson, C. Magnus

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