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Metastable Structures in Al Thin Films Before the Onset of Corrosion Pitting as Observed using Liquid Cell Transmission Electron Microscopy

Published online by Cambridge University Press:  25 February 2014

See Wee Chee ,
David J. Duquette ,
Frances M. Ross  and
Robert Hull
See Wee Chee*
Affiliation:
Department of Materials Science and Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180, USA
David J. Duquette
Affiliation:
Department of Materials Science and Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180, USA
Frances M. Ross
Affiliation:
IBM TJ Watson Research Center, Yorktown Heights, NY 10598, USA
Robert Hull
Affiliation:
Department of Materials Science and Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180, USA
*
*Corresponding author. [email protected]
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Abstract

One of the fundamental challenges in understanding the early stages of corrosion pitting in metals protected with an oxide film is that there are relatively few techniques that can probe microstructure with sufficient resolution while maintaining a wet environment. Here, we demonstrate that microstructural changes in Al thin films caused by aqueous NaCl solutions of varying chloride concentrations can be directly observed using a liquid flow cell enclosed within a transmission electron microscope (TEM) holder. In the absence of chloride, Al thin films did not exhibit significant corrosion when immersed in de-ionized water for 2 days. However, introducing 0.01 M NaCl solutions led to extensive random formation of blisters over the sample surface, while 0.1 M NaCl solutions formed anomalous structures that were larger than the typical grain size. Immersion in 1.0 M NaCl solutions led to fractal corrosion consistent with previously reported studies of Al thin films using optical microscopy. These results show the potential of in situ liquid cell electron microscopy for probing the processes that take place before the onset of pitting and for correlating pit locations with the underlying microstructure of the material.

Keywords

in situ electron microscopyaluminumthin filmscorrosionpitting
Type
In Situ Special Section
Information
Microscopy and Microanalysis , Volume 20 , Issue 2 , April 2014 , pp. 462 - 468
Copyright
© Microscopy Society of America 2014 

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Footnotes

†

Current address: Hummingbird Scientific, Lacey, WA 98516, USA

References

Abd-El-Nabey, B., Khalil, N. & Khamis, E. (1984). Alkaline corrosion of aluminium in water-organic solvent mixtures. Surf Technol 22, 367–376.Google Scholar
Abd-El-Nabey, B., Khalil, N. & Khamis, E. (1985). The acid corrosion of aluminium in water-organic solvent mixtures. Corros Sci 25, 225–232.CrossRefGoogle Scholar
Balázs, L. (1996). Corrosion front roughening in two-dimensional pitting of aluminum thin layers. Phys Rev E 54, 1183–1189.CrossRefGoogle ScholarPubMed
Balazs, L. & Gouyet, J. (1995). Two-dimensional pitting corrosion of aluminium thin layers. Physica A 217, 319–338.CrossRefGoogle Scholar
Bargeron, C. & Givens, R. (1980). Precursive blistering in the localized corrosion of aluminum. Corrosion 36, 618–625.CrossRefGoogle Scholar
Chee, S.W., Hull, R. & Ross, F.M. (2012). Liquid cell TEM of the corrosion of metal films in aqueous solutions. Microsc Microanal 18(Suppl 2), 1110–1111.Google Scholar
Chee, S.W., Ross, F.M., Duquette, D. & Hull, R. (2013). Studies of corrosion of Al thin films using liquid cell transmission electron microscopy. MRS Proceedings 1525, mrsf12–1525–ss11–03.Google Scholar
De Jonge, N. & Ross, F.M. (2011). Electron microscopy of specimens in liquid. Nat Nanotechnol 6, 695–704.CrossRefGoogle ScholarPubMed
Frankel, G. (1997). Pit growth in thin metallic films. Mater Sci Forum 247, 1–8.Google Scholar
Frankel, G.S. (1998). Pitting corrosion of metals. J Electrochem Soc 145, 2186–2198.CrossRefGoogle Scholar
Frankel, G. & Sridhar, N. (2008). Understanding localized corrosion. Mater Today 11, 38–44.CrossRefGoogle Scholar
Holtz, M.E., Yu, Y., Gao, J., Abruna, H.D. & Muller, D.A. (2013). In situ electron energy loss spectroscopy in liquids. Microsc Microanal 19, 1027–1035.Google Scholar
Klein, K.L., Anderson, I.M. & de Jonge, N. (2011). Transmission electron microscopy with a liquid flow cell. J Microsc 242, 117–123.CrossRefGoogle ScholarPubMed
Malladi, S.R.K., Tichelaar, F.D., Xu, Q., Wu, M.Y., Terryn, H., Mol, J.M.C., Hannour, F. & Zandbergen, H.W. (2013). Quasi in situ analytical TEM to investigate electrochemically induced microstructural changes in alloys: AA2024-T3 as an example. Corros Sci 69, 221–225.Google Scholar
Malladi, S.R.K., Xu, Q., Tichelaar, F.D., Zandbergen, H.W., Hannour, F., Mol, J.M.C. & Terryn, H. (2012). Early stages during localized corrosion of AA2024 TEM specimens in chloride environment. Surf Interface Anal 45, 1619–1625.Google Scholar
McCafferty, E. (2003). Sequence of steps in the pitting of aluminum by chloride ions. Corros Sci 45, 1421–1438.Google Scholar
Natishan, P.M., McCafferty, E. & Hubler, G.K. (1989). Localized corrosion behavior of aluminum surface alloys produced by ion implantation and ion beam mixing. Mater Sci Eng 116, 41–46.CrossRefGoogle Scholar
Noh, K.W., Liu, Y., Sun, L. & Dillon, S.J. (2012). Challenges associated with in-situ TEM in environmental systems: The case of silver in aqueous solutions. Ultramicroscopy 116, 34–38.Google Scholar
Szklarska-Smialowska, Z. (1999). Pitting corrosion of aluminum. Corros Sci 41, 1743–1767.Google Scholar
Unocic, R., Adamczyk, L., Dudney, N., Alsem, D., Salmon, N. & More, K. (2011). In-situ TEM characterization of electrochemical processes in energy storage systems. Microsc Microanal 17(Suppl 2), 1564–1565.Google Scholar
Williamson, M.J., Tromp, R.M., Vereecken, P.M., Hull, R. & Ross, F.M. (2003). Dynamic microscopy of nanoscale cluster growth at the solid-liquid interface. Nat Mater 2, 532–536.Google Scholar
Woehl, T.J., Jungjohann, K.L., Evans, J.E., Arslan, I., Ristenpart, W.D. & Browning, N.D. (2013). Experimental procedures to mitigate electron beam induced artifacts during in situ fluid imaging of nanomaterials. Ultramicroscopy 127, 53–63.Google Scholar