Towards Cr(VI)-free anodization of aluminum alloys for aerospace adhesive bonding applications: A review

doi:10.1007/s11705-017-1641-3

Front. Chem. Sci. Eng.

2017, Vol. 11

Issue (3) : 465-482 https://doi.org/10.1007/s11705-017-1641-3

REVIEW ARTICLE

Towards Cr(VI)-free anodization of aluminum alloys for aerospace adhesive bonding applications: A review

Shoshan T. Abrahami^1,², John M. M. de Kok³, Herman Terryn^2,⁴, Johannes M. C. Mol²(

)

¹. Materials innovation institute (M2i), 2628 XG, Delft, The Netherlands
². Delft University of Technology, Department of Materials Science and Engineering, 2628 CD, Delft, The Netherlands
³. Fokker Aerostructures BV, 3351 LB, Papendrecht, The Netherlands
⁴. Department of Materials and Chemistry, Research Group Electrochemical and Surface Engineering (SURF), Vrije Universiteit Brussel, 1050 Brussels, Belgium

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Abstract

For more than six decades, chromic acid anodizing (CAA) has been the central process in the surface pre-treatment of aluminum for adhesively bonded aircraft structures. Unfortunately, this electrolyte contains hexavalent chromium (Cr(VI)), a compound known for its toxicity and carcinogenic properties. To comply with the new strict international regulations, the Cr(VI)-era will soon have to come to an end. Anodizing aluminum in acid electrolytes produces a self-ordered porous oxide layer. Although different acids can be used to create this type of structure, the excellent adhesion and corrosion resistance that is currently achieved by the complete Cr(VI)-based process is not easily matched. This paper provides a critical overview and appraisal of proposed alternatives to CAA, including combinations of multiple anodizing steps, pre- and post anodizing treatments. The work is presented in terms of the modifications to the oxide properties, such as morphological features (e.g., pore size, barrier layer thickness) and surface chemistry, in order to evaluate the link between fundamental principles of adhesion and bond performance.

Keywords aluminum Cr(VI)-free surface pre-treatments anodizing adhesive bonding

Corresponding Author(s): Johannes M. C. Mol

Just Accepted Date: 07 April 2017 Online First Date: 16 May 2017 Issue Date: 23 August 2017

Cite this article:

Shoshan T. Abrahami,John M. M. de Kok,Herman Terryn, et al. Towards Cr(VI)-free anodization of aluminum alloys for aerospace adhesive bonding applications: A review[J]. Front. Chem. Sci. Eng., 2017, 11(3): 465-482.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-017-1641-3
https://academic.hep.com.cn/fcse/EN/Y2017/V11/I3/465

Fig.1 The production of metal-to-metal bonding at Fokker Aerostructures: (a) surface pre-treatment (panels hanging above the anodizing bath), (b) parts drying on the rack after pre-treatment, (c) primer application, (d) adhesive application, (e) a bonded part

Fig.2 Schematic illustration of the possible failure modes in structural adhesive joint: (A) cohesive fracture of the adhesive film, (B) interfacial disbonding between adhesive and primer, (C) cohesive fracture of primer layer, (D) interfacial disbonding between primer and anodic coating, (E) fracture within anodic oxide coating and (F) corrosion of aluminum substrate at metal/oxide interface and (G) failure of the metal substrate

Fig.3 Schematic illustration of the modified composition of the aluminum alloy surface present after metallurgical processing [22]

Fig.4 Schematic representations of the process steps and the modifications that take place during the complete Cr-based pre-treatment that is currently applied in the European aerospace industry

Fig.5 Schematic representation of the aluminum/electrolyte interface, showing the ionic processes involved in oxide growth during anodizing [30]

Fig.6 An idealized illustration of the anodic oxide structure formed on clad alloys following the 40/50 V CAA process [33]

Fig.7 Cross section of the anodic oxide produced on 2024-T3 clad by (a) TSA+PSA process¹⁾ and (b) PSA dynamic anodizing, with voltage decrease from 18 V to 9 V [59]

Fig.8 Cross section of AA2024-T3 clad after EPAD and SAA [62]

Tab.1 Anodizing parameters [63]

Fig.9 High-resolution SEM micrograph after boiling water treatment on AA2024-T3 clad for (a) 30 s, (b) 60 min and (c) 240 min. Edited from [72]

Tab.2 Percentage of incorporated anions in the porous oxide layer [76]

Fig.10 Schematic representations of the sectional and plan views of, respectively: (a) the duplex and (b) triplex structures of porous alumina cell walls formed in sulfuric and phosphoric acids, respectively [76]

Fig.11 Schematic representation of an ideally hexagonal columnar cell of a porous anodic alumina film [86]

Fig.12 SEM of the oxide layer depending on the bath temperature and the dwell time- surface views (anodizing potential E= 50 VSCE) [92]. Longer time and higher temperatures lead to their collapse and the formation of a ‘bird’s nest’

Fig.13 CAA 40/50 V processed, 2024-T3 bare: (a) plan view and (b) cross-section; 2024-T3 clad: (c) plan view and (d) cross-section. Reprinted from [62]. Copyright (2016), with permission from Elsevier

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