Synergistic Effect of Mo, W, Mn and Cr on the Passivation Behavior of a Fe-Based Amorphous Alloy Coating

doi:10.1007/s40195-017-0604-5

摘要/Abstract

Abstract:

In this work, the electrochemical behaviors of SAM2X5 Fe-based amorphous alloy coating and hard chromium coating were comparatively studied in 3.5 wt% NaCl solution. In comparison with the hard chromium coating, the SAM2X5 coating exhibited a wider and stable passive region with lower passive current density in the potentiodynamic polarization and showed a considerably lower current density at different anodic potentials in the potentiostatic polarization. In order to understand the passivation mechanism of the Fe-based amorphous coating, the components of the passive films formed at various polarization potentials were examined by X-ray photoelectron spectroscopy. The synergistic effect of Mo, W, Mn and Cr in the passive films was systemically analyzed. It has been revealed that Mo and W facilitate the formation of compact and stable Cr₂O₃ passive film at lower potentials, and the substantial enrichment of Mn in the passive film enhances the passivation ability at relatively higher potentials. The deep understanding of the passivation characteristics in multicomponent alloy systems could provide a guide for the design of corrosion-resistant amorphous alloy coatings for engineering applications.

Key words: Amorphous alloy, Metallic coating, Passivation, Surface film, X-ray photoelectron spectroscopy (XPS)

. [J]. Acta Metallurgica Sinica (English Letters), 2018, 31(3): 308-320.

Wan-Ping Tian, Hong-Wang Yang, Suo-De Zhang. Synergistic Effect of Mo, W, Mn and Cr on the Passivation Behavior of a Fe-Based Amorphous Alloy Coating[J]. Acta Metallurgica Sinica (English Letters), 2018, 31(3): 308-320.

图/表 14

Fig. 1 Typical SEM micrographs of the surface a, the cross section b for the SAM2X5 amorphous coating prepared by HVAF method

Fig. 2 XRD pattern of the SAM2X5 Fe-based amorphous coating. Inset DSC continuous heating curve of the coating

Fig. 3 Potentiodynamic polarization curves of the SAM2X5 Fe-based amorphous coating a, hard chromium coating b in 3.5 wt% NaCl solution

Fig. 4 Potentiostatic polarization curves of the hard chromium coatings (I) and the SAM2X5 Fe-based amorphous coatings (II) in 3.5 wt% NaCl solution for 100 min at: a 0.0 VSCE, b 0.6 VSCE, c 0.8 VSCE

Fig. 5 XPS survey spectra for SAM2X5 Fe-based amorphous coatings anodic polarized at 0 VSCE, 0.6 VSCE and 0.8 VSCE in 3.5 wt% NaCl solution

Fig. 6 The detailed XPS spectra of Cr 2p 3/2 of the passive films formed on the SAM2X5 Fe-based amorphous coatings a, c, e and the hard chromium coatings b, d, f after potentiostatic polarization at 0.0 VSCE a, b, 0.6 VSCE c, d, 0.8 VSCE e, f for 100-min in 3.5 wt% NaCl solution

Fig. 7 The detailed XPS spectra of Fe 2p 3/2 a, c, e, Mn 2p 3/2 b, d, f of the passive films formed on the SAM2X5 Fe-based amorphous coatings after polarization at 0.0 VSCE a, d, 0.6 VSCE c, d, 0.8 VSCE e, f for 100 min in 3.5 wt% NaCl solution

Fig. 8 The detailed XPS spectra of Mo 3d a, c, e, W 4f b, d, f of the passive films formed on the SAM2X5 Fe-based amorphous coatings after polarization at 0.0 VSCE a, b, 0.6 VSCE c, d, 0.8 VSCE e, f for 100 min in 3.5 wt% NaCl solution

Table 1 XPS peak position and peak assignment for the components of the passive films formed on the Fe-based amorphous coating surface

Spectra	Peak assignment		Peak position (eV)
Fe 2p _3/2	Fe(0)		706.5
	FeO		709.3
	Fe₂O₃		710.9
	Fe₃O₄	FeO	708.2
	Fe₃O₄	Fe₂O₃	710.3
Cr 2p _3/2	Cr(0)		573.8
	Cr₂O₃		575.9
	Cr(OH)₃		577.1
	Cr₇C₃		575.0
Mo 3d _3/2	Mo(0)		227.4
	MoO₂		228.7
	MoO₃		232.0
W 4f _5/2	W(0)		30.5
	WO₂		33.0
	WO₃		34.9
Mn 2p _3/2	Mn(0)		638.4
	MnO		640.5
	Mn₂O₃		642.2

Fig. 9 Depth profiles of the surface layer of SAM2X5 amorphous coatings after exposure to 3.5 wt% NaCl solution for 100 min. The vertical dash lines indicate the boundaries for the different samples at various potentials

Fig. 10 Cations fraction of Fe, Cr, Mo, W and Mn in the passive films formed on the SAM2X5 Fe-based amorphous coating after polarized at various potentials for 100 min

Table 2 Cationic fractions of detected corrosion-resistant elements by XPS for the Fe-based amorphous coating

Applied potential	Cationic fractions of the components in the passive film
Applied potential	Cr₂O₃	Cr(OH)₃	MoO₂	MoO₃	WO₂	WO₃	MnO	MnO₂	FeO	Fe₂O₃
0.0 V_SCE	0.703	0.297	0.578	0.422	0.521	0.574	0.246	0.754	0.602	0.398
0.6 V_SCE	0.322	0.678	0.164	0.836	0.189	0.0811	0.342	0.658	0.538	0.462
0.8 V_SCE	0.669	0.331	0	1	0	1	0.527	0.423	0.732	0.268

Fig. 11 Proportion of Mn to the corrosion-resistant elements (Fe, Cr, Mo, W and Mn) in the passive films formed on the SAM2X5 Fe-based amorphous coatings after polarized at various potentials for 100-min in 3.5 wt% NaCl solution

Fig. 12 Schema of the synergistic effect of Mo, W, Mn and Cr on the passivation behavior in multicomponent Fe-based amorphous alloys during the anodic polarization in a chloride-containing solution

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