Al2O3 Coatings Deposited By ALD on Al Alloys

Wednesday, October 14, 2015: 14:40
102-A (Phoenix Convention Center)
P. Marcus, J. Tao, J. Swiatowska (CNRS Chimie ParisTech/IRCP/PCS), S. Zanna (CNRS Chimie ParisTech/IRCP/PCS), A. Seyeux (CNRS Chimie ParisTech), E. Harkonen (University of Helsinki, Finland), and M. Ritala (University of Helsinki, Finland)
The key question that was addressed in this work is the following: would a uniform surface layer of aluminium oxide on aluminium alloys be protective against corrosion despite the presence of intermetallic Al-Cu particles?

To answer this question, well defined aluminium oxide coatings were deposited by atomic layer deposition (ALD) on the surface of a model binary aluminium-copper alloy (Al-Cu5%wt.)  in which copper-rich particles were produced by ageing.

The corrosion resistance of uncoated, mechanically polished aluminium alloy samples covered by a native oxide layer was compared with the one of aluminium alloy samples protected by a 20 nm thick Al2Olayer deposited by Atomic Layer Deposition (ALD). Detailed surface analysis was performed by X-ray Photoelectron Spectroscopy (XPS), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and Scanning Electron Microscopy (SEM) on the samples before and after immersion in 0.01M NaCl + 0.3 % vol. H2O2 (pH=6.2).

The polished Al-Cu alloy with a thin native oxide layer (around 5 nm, as measured by XPS), exhibits a copper enrichment at the oxide/Al alloy interface, clearly evidenced by ToF-SIMS depth profiling. The ToF-SIMS chemical images and EDX analysis confirmed the presence of copper-rich intermetallics (Al2Cu) in the interfacial oxide/substrate region. A short immersion (~7 min) of this alloy in a near neutral NaCl solution lead to severe surface modifications: formation of mixed aluminium-copper oxide layer rich in CuO and Cu(OH)2 (as shown by XPS), and formation of an inhomogeneous, thick aluminium oxide deposit (as shown by SEM and ToF-SIMS imaging). Localized corrosion in the vicinity of the intermetallic particles (well known as trenching around particles) is clearly observed by SEM and ToF-SIMS imaging.

A significant improvement on corrosion resistance was observed after deposition of the 20 nm-thick Al2O3 ALD coating. Despite the presence of intermetallics at the oxide/substrate interface (observed in the SEM) no significant corrosion occurred in the chloride solution, the Al2Cu particles remained intact, and no trenching around them was observed.

 In conclusion, the formation of a good quality alumina layer on the Al-5%Cu alloy is beneficial for its corrosion resistance. The coating can be deposited by ALD without prior removal of the intermetallic particles.