Low-valence ion addition induced more compact passive films on nickel-copper nano-coatings

doi:10.1016/j.jmst.2019.05.051

Abstract

Abstract:

Ni-Cu nano-coatings were prepared by pulsed electroplating technique in the baths containing various amount of boric acid. Their microstructure, morphologies and corrosion resistance were characterized in detail. The addition of boric acid strongly influences on the microstructure of the Ni-Cu coatings. The coating with a grain size of 130 nm, obtained from the bath containing 35 g L^-1 boric acid, shows the highest corrosion resistance. This is attributed to the low-valence Cu ion (Cu⁺) additions in nickel oxide, which could significantly decrease the oxygen ion vacancy density in the passive film to form a more compact passive film. The higher Cu⁺ additions and the lower diffusivity of point defects (D₀) are responsible for the formation of more compact passive film on the coating obtained from the bath with 35 g L^-1 boric acid.

Key words: Passive film, Point defect, Corrosion, Electroplating, Coating

Quangquan Do, Hongze An, Guozhe Meng, Weihua Li, Lai-Chang Zhang, Yangqiu Wang, Bin Liu, Junyi Wang, Fuhui Wang. Low-valence ion addition induced more compact passive films on nickel-copper nano-coatings[J]. J. Mater. Sci. Technol., 2019, 35(10): 2144-2155.

Figures/Tables 22

Fig. 1. SEM surface morphologies of Ni-Cu coatings synthesized from the baths containing (a) 15 g L-1, (b) 25 g L-1, (c) 35 g L-1 and (d) 45 g L-1 boric acid.

Fig. 2. SEM images of cross-sectional morphologies of Ni-Cu coatings synthesized from baths with (a) 15 g L-1, (b) 25 g L-1, (c) 35 g L-1 and (d) 45 g L-1 boric acid.

Fig. 3. Elemental mapping for element distribution in the coatings synthesized from the baths with (a, b, c) 15 g L-1, (d, e, f) 25 g L-1, (g, h, i) 35 g L-1 and (j, k, l) 45 g L-1 boric acid.

Fig. 4. TEM images and corresponding diffraction patterns (insets) of the Ni-Cu coatings synthesized from the baths with (a) 15 g L-1, (b) 25 g L-1, (c) 35 g L-1 and (d) 45 g L-1 boric acid. The diffraction patterns in insets indicate the formation of nanostructured single γ phase.

Fig. 5. XRD patterns for Ni-Cu nanocomposite coatings synthesized from bath with 15, 25, 35 and 45 g L-1 boric acid.

Fig. 6. Statistical distributions for grain size of the nanocrystals of nickel-copper coatings synthesized from the bath with (a) 15 g L-1, (b) 25 g L-1, (c) 35 g L-1 and (d) 45 g L-1 boric acid.

Fig. 7. Potentiodynamic polarization curves of the coatings obtained from the baths with various boric concentrations in 0.3 M NaCl solution at 25 ± 1 °C.

Table 1 Electrochemical parameters obtained by fitting potentiodynamic curves in Fig. 7 (icorr and ip are the corrosion and passive current density, respectively; Ecorr and Epit are the corrosion and pitting potential, respectively).

Boric acid (g L^-1)	E_corr (mV_SHE)	i_corr (μA cm^-2)	i_p (μA cm^-2)	E_pit (mV_SHE)
15	1.6	0.61	4.1	196
25	45	0.52	2.7	284
35	50	0.13	2.5	335
45	44	0.55	3.2	195

Fig. 8. Nyquist plots of nano-coatings. The inset in shows the corresponding equivalent electrical circuit. RS is the solution resistance, CPEf is CPE which expresses the passive film capacitance and Rfilm is passive film resistance, CPEdl is also the CPE which expresses the double layer capacitance and Rt expresses the charge transfer resistance of Ni-Cu coatings, respectively.

Table 2 Key electrochemical parameters obtained by fitting the EIS data in Fig. 8 (RS is the solution resistance, CPEf is the constant phase element (CPE) of the passive film capacitance, Rfilm is the passive film resistance, CPEdl is the CPE of the double layer capacitance and Rt is the charge transfer resistance on the matrix surface).

Boric acid (g L^-1)	R_S (Ω cm²)	CPE_f (×10^-5 S s-ⁿ cm^-2)	n₁	R_film (kΩ cm²)	CPE_dl (×10^-5 S s-ⁿ cm^-2)	n₂	R_t (kΩ cm²)
15	14.45	1.798	0.954	16.25	3.491	0.7745	23.68
25	15.87	2.035	0.9602	41.42	1.92	0.5877	64.05
35	15.51	1.734	0.9472	52.25	0.825	0.4286	111.9
45	14.11	1.68	0.96	20.85	3.156	0.7564	29.17

Fig. 9. Relationship between the charge transfer resistance (Rt) of the Ni-Cu nano-coatings and boric concentration (g L-1) in the electrolyte.

Fig. 10. XPS survey spectra of the passive films formed on the Ni-Cu nanostructured coatings synthesized from baths with (a) 25 g L-1 and (b) 35 g L-1 boric acid after passivation 30 min at 0.15 VSHE in 0.3 M NaCl solution.

Fig. 11. Core-level spectra of Ni2p3/2 for the passive films formed on the Ni-Cu nanostructured coatings synthesized from baths with (a) 25 g L-1 and (b) 35 g L-1 boric acid after passivation 30 min at 0.15 VSHE in 0.3 M NaCl solution.

Fig. 12. Core-level spectra of Cu2p3/2 for the passive films formed on the Ni-Cu nanostructured coatings synthesized from baths with (a) 25 g L-1 and (b) 35 g L-1 boric acid after passivation 30 min at 0.15 VSHE in 0.3 M NaCl solution.

Table 3 Atomic percentage (at.%) of nano coatings after passivation 30 min at 0.15 VSHE in 0.3 M NaCl solution.

Boric acid (g L^-1)	Cu2p3/2		Ni2p3/2
Boric acid (g L^-1)	CuO (%)	Cu₂O (%)	Ni(OH)₂ (%)	NiO (%)
25	63.38	36.62	47.36	52.64
35	51.06	48.94	21.67	78.33

Fig. 13. M-S plots of the passive films formed the on Ni-Cu nanostructured coatings synthesized from baths with (a) 25 g L-1 and (b) 35 g L-1 boric acid in 0.3 M NaCl solution after 30 min passivation at 75, 100, 125, 150, 175 and 200 mVSHE.

Table 4 Carrier densities Nd (×1021 cm-3) of the passive film formed on the Ni-Cu coatings in 0.3 M NaCl solution after 30 min passivation at 75, 100, 125, 150, 175 and 200 mVSHE.

Potential (mV_SHE)	Concentration of Boric acid (g L^-1)
Potential (mV_SHE)	25	35
75	2.81	2.31
100	2.94	2.4
125	2.97	2.48
150	3.14	2.53
175	3.65	2.78
200	3.94	3.01

Fig. 14. Nd-Ef curves and their fitting curves of the passive film formed on the Ni-Cu nanostructured coatings synthesized from baths with (a) 25 g L-1 and (b) 35 g L-1 boric acid.

Fig. 15. Potentiostatic current transients for the passive films formed on the Ni-Cu nanostructured coatings synthesized from baths with (a) 25 g L-1 and (b) 35 g L-1 boric acid, measured by the potential at 75, 100, 125, 150, 175 and 200 mVSHE in 0.3 M NaCl solution. The insets show the steady state current density through passive films formed on these coatings for 1800s at various film formation potentials in 0.3 M NaCl solution.

Fig. 16. Lss-Ef and their fitting liners of the passive film formed on the Ni-Cu coatings for 1800s at various film formation potentials in 0.3 M NaCl solution.

Fig. A1 Surface morphology of Ni-Cu nano alloy coatings synthesized from bath with (a)15, (b) 25, (c) 35 and (d) 45 g L-1 boric acid after potentiodynamic polarization.

Fig. A2 The core-level spectra of Cl 2p for the passive films formed on the Ni-Cu nanostructured coatings synthesized from bath with (a) 25 and (b) 35 g L-1 boric acid after passivation 30 min at 0.15 VSHE in 0.3 M NaCl solution.

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