Spontaneous Aryldiazonium Film Formation on 440C Stainless Steel in Nonaqueous Environments
Abstract
The ability of three aryldiazonium salts to spontaneously assemble onto the surface of type 440C stainless steel is investigated in acetonitrile and the model hydraulic fluids tributyl phosphate and hexamethyldisiloxane. Competition between native oxide growth and organic film growth at different diazonium salt concentrations is monitored by electrochemical impedance spectroscopy. At 1 mM diazonium salt, 70% of total assembly is complete within 10 minutes, though total surface coverage by organics is limited to ≈ 0.15 monolayers. X-ray photoelectron spectroscopy confirms preferential bonding of organic molecules to iron over chromium, and adsorption of BF-4 onto the surface. Secondary ion mass spectroscopy reveals the ability of these films to self-heal when mechanically removed or damaged. Aging the diazonium salts in these nonaqueous environments demonstrates that up to 90% of the original diazonium salt concentration remains after 21 days at room temperature, while increasing the temperature beyond 50 °C results complete decomposition within 24 hours, regardless of solvent-salt combination.
- Authors:
-
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- The Boeing Company
- OSTI Identifier:
- 1184478
- Report Number(s):
- SAND-2014-18685J
Journal ID: ISSN 0743-7463; 540290
- Grant/Contract Number:
- AC04-94AL85000
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Langmuir
- Additional Journal Information:
- Journal Volume: 30; Journal Issue: 47; Journal ID: ISSN 0743-7463
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
Citation Formats
Small, Leo J., Hibbs, Michael R., and Wheeler, David R. Spontaneous Aryldiazonium Film Formation on 440C Stainless Steel in Nonaqueous Environments. United States: N. p., 2014.
Web. doi:10.1021/la503630f.
Small, Leo J., Hibbs, Michael R., & Wheeler, David R. Spontaneous Aryldiazonium Film Formation on 440C Stainless Steel in Nonaqueous Environments. United States. https://doi.org/10.1021/la503630f
Small, Leo J., Hibbs, Michael R., and Wheeler, David R. Fri .
"Spontaneous Aryldiazonium Film Formation on 440C Stainless Steel in Nonaqueous Environments". United States. https://doi.org/10.1021/la503630f. https://www.osti.gov/servlets/purl/1184478.
@article{osti_1184478,
title = {Spontaneous Aryldiazonium Film Formation on 440C Stainless Steel in Nonaqueous Environments},
author = {Small, Leo J. and Hibbs, Michael R. and Wheeler, David R.},
abstractNote = {The ability of three aryldiazonium salts to spontaneously assemble onto the surface of type 440C stainless steel is investigated in acetonitrile and the model hydraulic fluids tributyl phosphate and hexamethyldisiloxane. Competition between native oxide growth and organic film growth at different diazonium salt concentrations is monitored by electrochemical impedance spectroscopy. At 1 mM diazonium salt, 70% of total assembly is complete within 10 minutes, though total surface coverage by organics is limited to ≈ 0.15 monolayers. X-ray photoelectron spectroscopy confirms preferential bonding of organic molecules to iron over chromium, and adsorption of BF-4 onto the surface. Secondary ion mass spectroscopy reveals the ability of these films to self-heal when mechanically removed or damaged. Aging the diazonium salts in these nonaqueous environments demonstrates that up to 90% of the original diazonium salt concentration remains after 21 days at room temperature, while increasing the temperature beyond 50 °C results complete decomposition within 24 hours, regardless of solvent-salt combination.},
doi = {10.1021/la503630f},
journal = {Langmuir},
number = 47,
volume = 30,
place = {United States},
year = {Fri Nov 07 00:00:00 EST 2014},
month = {Fri Nov 07 00:00:00 EST 2014}
}
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