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Application of copper corrosion inhibitors in mineral oil: Surface analytical studies and corrosion mitigation evaluations
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This doctoral thesis explores the copper corrosion inhibiting properties of a number of nitrogen containing hetero-organic compounds in refined mineral oil. Traditional organic corrosion inhibitors, as well as novel and bioorganic compounds have been studied.

The Hansen solubility parameters were determined for the three commercial organic corrosion inhibitors; benzotriazole, tolyltriazole and Irgamet 39™, an N-(aminomethyl) substituted triazole. The determination was done using an indirect method utilizing the solubility of the inhibitors in various solvents. The calculated Hansen solubility parameters of the inhibitors were compared with the Hansen solubility parameters and solubility sphere of refined mineral oil. The obtained Hansen solubility parameters of benzotriazole indicate very low solubility in mineral oils, while the solubility of tolyltriazole was slightly higher due to the methyl substitution. The obtained Hansen solubility parameters of Irgamet 39™ indicate full miscibility with refined mineral oil. The adsorption kinetics of the inhibitors on copper surfaces in refined mineral oil was studied by means of in situ ellipsometry and related to the Hansen solubility parameters. A good correlation was seen; the compound with the highest solubility (Irgamet 39™) generated the thinnest film, while the greatest film thickness was seen for the molecule with the lowest solubility (benzotriazole).

The issue of decomposition of the N-(aminomethyl) substituted Irgamet 39™ and Irgamet 30™ upon adsorption was addressed and analysed by using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The ToF-SIMS study revealed that both compounds appeared to lose their aminomethyl tails upon adsorption. No signals from the intact molecules were detected.

The possibility of utilising bio-organic substances as organic corrosion inhibitors has been examined. The copper corrosion inhibiting effects of four bioorganic compounds; adenine, purine, cysteine and histidine were studied by in situ ellipsometry, copper dissolution, and a standardised industrial corrosion test developed by the International Electrotechnical Commission (IEC 62535). Adenine and purine were found to adequately mitigate copper corrosion, while cysteine and histidine were found to have low, or even accelerating, effects on the corrosion rate.

The corrosion inhibiting properties of five benzo-fused azoles; benzotriazole, benzimidazol, indole, benzothiazole and benzothiadiazole in refined mineral oil were analysed by means of ellipsometry, ToF-SIMS, copper dissolution studies and the standardised industrial corrosion test (IEC 62535). It was demonstrated that copper corrosion was mitigated by the addition of benzotriazole and benzimidazole. However, addition of indole, benzothiazole and benzothiadiazole did not generate any significant corrosion mitigating effect. In general, the corrosion inhibition efficiency of the investigated molecules was found to decrease with increased polarizability of the molecule.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. , viii, 61 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2012:33
National Category
Corrosion Engineering
Identifiers
URN: urn:nbn:se:kth:diva-101316ISBN: 978-91-7501-433-3 (print)OAI: oai:DiVA.org:kth-101316DiVA: diva2:547091
Public defence
2012-09-28, F3, Lindstedtsvägen 26, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20120829

Available from: 2012-08-29 Created: 2012-08-27 Last updated: 2012-08-29Bibliographically approved
List of papers
1. Determination of three-dimensional solubility parameters and solubility spheres for naphthenic mineral oils
Open this publication in new window or tab >>Determination of three-dimensional solubility parameters and solubility spheres for naphthenic mineral oils
2008 (English)In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029, Vol. 22, no 5, 3395-3401 p.Article in journal (Refereed) Published
Abstract [en]

The Hansen solubility parameters were determined for three hydrocarbon fluids, equivalent to naphthenic mineral oil of different degrees of refinement. This was done by an indirect method based on the solubility of the hydrocarbon fluids in a system of solvents with known Hansen solubility parameters. It was concluded that the method may serve is a tool to estimate the approximate solubility parameters of naphthenic oil. However, in this study, the accuracy was insufficient to separate naphthenic oil of different degrees of refinement.

National Category
Engineering and Technology
Identifiers
urn:nbn:se:kth:diva-101070 (URN)10.1021/ef800256u (DOI)000259332600068 ()
Note
QC 20120822Available from: 2012-08-22 Created: 2012-08-22 Last updated: 2017-12-07Bibliographically approved
2. Determining the Hansen Solubility Parameter of Three Corrosion Inhibitors and the Correlation with Mineral Oil
Open this publication in new window or tab >>Determining the Hansen Solubility Parameter of Three Corrosion Inhibitors and the Correlation with Mineral Oil
(English)Article in journal (Other academic) Submitted
Identifiers
urn:nbn:se:kth:diva-101071 (URN)
Note

QS 2012

Available from: 2012-08-23 Created: 2012-08-22 Last updated: 2012-08-29Bibliographically approved
3. Adsorption and film growth of N-methylamino substituted triazoles on copper surfaces in hydrocarbon media
Open this publication in new window or tab >>Adsorption and film growth of N-methylamino substituted triazoles on copper surfaces in hydrocarbon media
2007 (English)In: Applied Surface Science, ISSN 0169-4332, E-ISSN 1873-5584, Vol. 254, no 5, 1528-1533 p.Article in journal (Refereed) Published
Abstract [en]

The adsorption of benzotriazole (BTA), tolyltriazole (TTA) and two different N-methylaminosubstituted triazoles on copper surfaces in hydrocarbon media has been examined by in situ ellipsometry and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). All four triazoles were found to form films and from the ellipsometric study were the film thicknesses estimated to be in the range of 0.5-2 nm after 1000 min exposure time. The layers formed from BTA and TTA were thicker (up to 2 nm) than the layers from N-aminomethyl substituted triazoles (roughly 0.5 nm). Desorption was studied qualitatively and 20% or less of the adsorbed material were found to desorb. The ToF-SIMS study showed that while BTA and TTA adsorbed intact did the N-aminomethyl substituted triazoles appear to loose their aminomethyl tails on binding since only signals corresponding to triazole moieties of the compounds were detected.

Keyword
Cu, Triazole, Inhibitor, Ellipsometry, ToF-SIMS
National Category
Materials Chemistry
Identifiers
urn:nbn:se:kth:diva-101075 (URN)10.1016/j.apsusc.2007.07.023 (DOI)000251899400029 ()
Note
QC 20120823Available from: 2012-08-23 Created: 2012-08-23 Last updated: 2017-12-07Bibliographically approved
4. Bioorganic compounds as copper corrosion inhibitors in hydrocarbon media
Open this publication in new window or tab >>Bioorganic compounds as copper corrosion inhibitors in hydrocarbon media
2012 (English)In: Corrosion Science, ISSN 0010-938X, E-ISSN 1879-0496, Vol. 58, 104-114 p.Article in journal (Refereed) Published
Abstract [en]

The corrosion protection of copper by four bioorganic compounds; adenine, purine, cysteine and histidine, in hydrocarbon media has been examined by in situ ellipsometry, atom absorption spectroscopy and a standard corrosion test. Adenine and purine were found to irreversibly bind to the copper surface. The amount of dissolved copper was severely lowered and the copper surface appeared unaffected. It was concluded that adenine and purine exhibited a surface passivating effect, whereas the effect of cysteine and histidine was significantly lower. The influence on oxidation stability of the medium by addition of the compounds was examined and found to be minor.

Keyword
Copper, Ellipsometry, Weight loss, Oxidation, Passive films
National Category
Metallurgy and Metallic Materials
Identifiers
urn:nbn:se:kth:diva-95490 (URN)10.1016/j.corsci.2012.01.009 (DOI)000302980100012 ()2-s2.0-84858622335 (Scopus ID)
Note
QC 20120528Available from: 2012-05-28 Created: 2012-05-28 Last updated: 2017-12-07Bibliographically approved
5. Inhibition of copper corrosion in mineral oil medium by benzofused azoles
Open this publication in new window or tab >>Inhibition of copper corrosion in mineral oil medium by benzofused azoles
(English)Manuscript (preprint) (Other academic)
Identifiers
urn:nbn:se:kth:diva-101076 (URN)
Note
QS 2012Available from: 2012-08-23 Created: 2012-08-23 Last updated: 2012-08-29Bibliographically approved

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