Inhibition of galvanic corrosion in Al/Cu coupling model by synergistic combination of 3-Amino-1,2,4-triazole-5-thiol and cerium chloride

doi:10.1016/j.jmst.2020.01.015

Abstract

Abstract:

A synergistic inhibition study was carried out on an aluminium/copper galvanic coupling model in neutral aerated NaCl solution using scanning vibrating electrode technique (SVET). The approach allows the simulation of the local micro-galvanic cells of AA2024-T3 obtained from the potential difference between the intermetallic particles (IMPs) and the aluminium matrix. The inhibition effect of CeCl₃ and 3-Amino-1,2,4-triazole-5-thiol (ATAT) was demonstrated by the reduction in the galvanic current density over Al and Cu surfaces. An improved inhibition from positive synergistic effect was revealed by the combination of the two inhibitors after 24 h of immersion, with the best inhibition recorded for Ce_1.5ATAT_3.5. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (ToF-SIMS) were used to characterize the Ce- and ATAT-based complex film formed and to illustrate the mechanism of inhibition.

Key words: Aluminium alloy, Galvanic corrosion, Neutral inhibition, Scanning vibrating electrode technique (SVET), X-ray photoelectron spectroscopy (XPS), Time of flight secondary ion mass spectrometry (ToF-SIMS)

Inime Ime Udoh, Hongwei Shi, Mohammad Soleymanibrojeni, Fuchun Liu, En-Hou Han. Inhibition of galvanic corrosion in Al/Cu coupling model by synergistic combination of 3-Amino-1,2,4-triazole-5-thiol and cerium chloride[J]. J. Mater. Sci. Technol., 2020, 44: 102-115.

Figures/Tables 16

Fig. 1. Schematic diagram and optical micrograph of Al/Cu coupling model.

Table 1 Name of sample and composition of electrolytes.

Sample	Electrolyte/inhibitor composition
Reference	50 mM NaCl
Ce₅	35 mM NaCl + 5 mM CeCl₃
ATAT₅	50 mM NaCl + 5 mM ATAT
Ce_2.5ATAT_2.5	42.5 mM NaCl + 2.5 mM CeCl₃ + 2.5 mM ATAT
Ce_1.5ATAT_3.5	45.5 mM NaCl + 1.5 mM CeCl₃ + 3.5 mM ATAT

Fig. 2. Distribution of galvanic corrosion current densities on the surface of Al/Cu couple immersed in aerated 50 mM aqueous NaCl reference solution. Scans obtained at (a) 0 h, (b) 2 h, and (c) 24 h of immersion; (d) optical image of sample after 24 h of immersion.

Fig. 3. Distribution of galvanic corrosion current densities on the surface of Al/Cu couple immersed in aerated 35 mM NaCl + 5 mM CeCl3 aqueous solution obtained at (a) 0 h, (b) 2 h, and (c) 24 h of immersion; (d) optical image of sample after 24 h of immersion.

Fig. 4. Distribution of galvanic corrosion current densities on the surface of Al/Cu couple immersed in aerated 50 mM NaCl + 5 mM ATAT aqueous solution obtained at (a) 0 h, (b) 2 h, and (c) 24 h of immersion; (d) optical image of sample after 24 h of immersion.

Fig. 5. Distribution of galvanic corrosion current densities on the surface of Al/Cu couple immersed in aerated 42.5 mM NaCl + 2.5 mM CeCl3 + 2.5 mM ATAT aqueous solution obtained at (a) 0 h, (b) 2 h, and (c) 24 h of immersion; (d) optical image of sample after 24 h of immersion.

Fig. 6. Distribution of galvanic corrosion current densities on the surface of Al/Cu couple immersed in aerated 45.5 mM NaCl + 1.5 mM CeCl3 + 3.5 mM ATAT aqueous solution obtained at (a) 0 h, (b) 2 h, and (c) 24 h of immersion; (d) optical image of sample after 24 h of immersion.

Fig. 7. Profiles of total anodic and cathodic currents from the surface of Al/Cu couple after immersion in different electrolytes for 24 h.

Table 2 Calculated values of inhibition efficiencies for the tested inhibitor systems.

Sample	Total current, I			Inhibition efficiency, η
	0 h	2 h	24 h	0 h	2 h	24 h
Reference	106.5	63.9	42.2	0	0	0
Ce₅	78	28.5	10.5	0.27	0.55	0.75
ATAT₅	32	9.5	9.5	0.7	0.85	0.77
Ce_2.5ATAT_2.5	46.7	11.6	6.4	0.56	0.82	0.85
Ce_1.5ATAT_3.5	0.8	0.3	0.2	0.99	0.99	0.99

Fig. 8. SEM images of Al and Cu surfaces of Al/Cu couple after 24 h of immersion in 50 mM NaCl solution for (a, b) reference, (c, d) Ce5, (e, f) ATAT5, (g, h) Ce2.5ATAT2.5, (i, j) Ce1.5ATAT3.5, respectively.

Fig. 9. XPS survey (a) of the Al surface of Al/Cu couple after 24 h of immersion in Ce2.5ATAT2.5 and sputtering time of 0 s, 30 s and 60 s, and corresponding spectra for Ce 2p (b) and N 1s (c).

Fig. 10. XPS survey (a) of the Cu surface of Al/Cu couple after 24 h of immersion in Ce2.5ATAT2.5 and sputtering time of 0 s, 30 s and 60 s, and corresponding spectra for Ce 2p (b) and N 1s (c).

Fig. 11. Fitting of XPS curve of N 1s (a) and Ce 3d (b) after sputtering time of 60 s obtained from Al and Cu surfaces of Al/Cu couple after 24 h of immersion in Ce2.5ATAT2.5.

Fig. 12. ToF-SIMS positive and negative spectra from the Al surface (a, b) and Cu surface (c, d) of Al/Cu couple after 24 h of immersion in Ce2.5ATAT2.5, respectively.

Fig. 13. ToF-SIMS negative profiles obtained from the Al surface (a) and Cu surface (b) of Al/Cu couple after 24 h of immersion in Ce2.5ATAT2.5.

Fig. 14. Logarithm of the activity of chemical species in solution in relation to pH for AA2024-T3 dissolution. The diagram was constructed using Hydra/Medusa software [59].

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