Corrosion Resistance and Electrochemical Behaviour of Amorphous Ni84.9Cr7.4Si4.2Fe3.5 Alloy in Alkaline and Acidic Solutions

doi:10.1007/s40195-019-00904-4

Abstract

Abstract:

In this work, the corrosion behaviours of the amorphous Ni_84.9Cr_7.4Si_4.2Fe_3.5 alloy and its crystalline counterpart are studied in acidic, neutral, and alkaline solutions by scanning electron microscopy, electrochemical impedance spectroscopy, and potentiodynamic and potentiostatic polarization tests. X-ray photoelectron spectroscopy and scanning Kelvin probe are employed to characterize the alloy surface. The results show that the amorphous Ni_84.9Cr_7.4Si_4.2Fe_3.5 alloy presents a better corrosion resistance compared to its crystalline counterpart, which is attributed to the uniform energy distribution of the atoms on the amorphous alloy surface, and this presents as a uniform electric potential map to effectively suppress the occurrence of the corrosion cell reaction.

Key words: Amorphous alloy, Corrosion, Electrochemical impedance spectroscopy, Potentiodynamic polarization, Scanning electron microscopy

Chao Han, Ying-Hua Wei, Hai-Feng Zhang, Zheng-Wang Zhu, Jing Li. Corrosion Resistance and Electrochemical Behaviour of Amorphous Ni_84.9Cr_7.4Si_4.2Fe_3.5 Alloy in Alkaline and Acidic Solutions[J]. Acta Metallurgica Sinica (English Letters), 2019, 32(11): 1421-1436.

Figures/Tables 25

Fig. 1 Images of a shiny upper side of, b copper wheel side of the amorphous Ni84.9Cr7.4Si4.2Fe3.5 alloy obtained by an optical microscope

Table 1 Composition of the sample examined via ICP-MS and AAS

	Ni	Cr	Si	Fe
ICP-MS	84.9	7.4	4.2	3.5
AAS	86.0	6.6	4.1	3.3

Fig. 2 XRD patterns of the amorphous Ni84.9Cr7.4Si4.2Fe3.5 alloy and its annealed sample

Fig. 3 TEM images and SAED patterns of the amorphous Ni84.9Cr7.4Si4.2Fe3.5 alloy

Fig. 4 DSC thermograms taken from the amorphous Ni84.9Cr7.4Si4.2Fe3.5 alloy

Fig. 5 Potentiodynamic polarization curves for 304 stainless steel, 316 stainless steel, amorphous Ni84.9Cr7.4Si4.2Fe3.5 alloy, and its annealed sample at a pH=13, b pH=12, c pH=11, d pH=7, e pH=3, f pH=1

Table 2 Results of potentiodynamic polarization tests performed on the Ni84.9Cr7.4Si4.2Fe3.5 alloy and stainless steel samples

pH value	Measured parameter	Amorphous Ni_84.9Cr_7.4Si_4.2Fe_3.5 alloy	Ni_84.9Cr_7.4Si_4.2Fe_3.5 alloy annealed at 973 K	304 SS	316 SS
13	E_corr (mV vs. SCE)	-193	-279	-506	-477
	I_corr (μA/cm²)	0.020	0.173	0.202	0.077
	v_corr (mm/y)	0.000213	0.001843	0.002995	0.000925
12	E_corr (mV vs. SCE)	-163	-232	-394	-405
	I_corr (μA/cm²)	0.016	0.200	0.265	0.091
	v_corr (mm/y)	0.000175	0.002131	0.003179	0.001088
11	E_corr (mV vs. SCE)	-131	-192	-409	-369
	I_corr (μA/cm²)	0.017	0.092	0.145	0.090
	v_corr (mm/y)	0.000181	0.000985	0.001548	0.001081
7	E_corr (mV vs. SCE)	-44	-188	-443	-419
	I_corr (μA/cm²)	0.016	0.338	0.063	0.034
	v_corr (mm/y)	0.000169	0.003596	0.000758	0.000406
3	E_corr (mV vs. SCE)	-109	-218	-416	-342
	I_corr (μA/cm²)	0.247	14.438	0.132	0.101
	v_corr (mm/y)	0.002639	0.153790	0.001583	0.001210
1	E_corr (mV vs. SCE)	-160	-197	-309	-374
	I_corr (μA/cm²)	0.927	18.393	7.238	9.932
	v_corr (mm/y)	0.009872	0.195920	0.086861	0.119190

Fig. 6 Nyquist plots of 304 SS, 316 SS, amorphous alloy, and its annealed sample in soak solutions and corresponding fitted results of EIS data at a pH=13, b pH=12, c pH=11, d pH=7, e pH=3, f pH=1

Fig. 7 Bode impedance magnitude plots of 304 SS, 316 SS, amorphous alloy, and its annealed sample in soak solutions and corresponding fitted results of EIS data at a pH=13, b pH=12, c pH=11, d pH=7, e pH=3, f pH=1

Fig. 8 Bode phase angle plots of 304 SS, 316 SS, amorphous alloy, and its annealed sample in soak solutions and corresponding fitted results of EIS data at a pH=13, b pH=12, c pH=11, d pH=7, e pH=3, f pH=1

Fig. 9 Equivalent circuit used to simulate the EIS data of the amorphous Ni84.9Cr7.4Si4.2Fe3.5 alloy tested at the pH values of 13, 12, 11, and 7

Table 3 Fitted values of the amorphous alloy

pH value of the soak solution	R_s (Ω cm²)	R₍_x₁₎ (Ω cm²)	R₍_x₂₎ (Ω cm²)	Q₍_x₁₎ (μΩ^-1 cm^-2 sⁿ)	Q₍_x₂₎ (μΩ^-1 cm^-2 sⁿ)	n ₍_x₁₎	n ₍_x₂₎
13	10.60	2.32×10¹⁵	3.35×10¹⁵	15.79	3.78	1.000	0.917
12	8.43	3.46×10¹⁵	4.63×10¹³	6.92	1.54	0.814	0.978
11	7.75	2.77×10¹³	1.40×10⁷	3.13	4.40	0.948	0.549
7	14.63	9.67×10¹²	1.12×10⁶	4.28	1.49	0.938	0.921

Fig. 10 EIS results for the amorphous alloy in the air and soaked in the NaOH solution for 7 days

Fig. 11 Equivalent circuit used to simulate the EIS data of the annealed sample tested at the pH values of 13, 12, 11, and 7

Table 4 Fitted values of the crystalline counterpart

pH value of the soak solution	R_s (Ω cm²)	R_pore (Ω cm²)	R_ct (Ω cm²)	Q_film (μΩ^-1 cm^-2 sⁿ)	Q_dl (μΩ^-1 cm^-2 sⁿ)	n _film	n _dl
13	5.81	8.49×10⁴	1.42×10⁴	8.00	254.00	0.944	1
12	5.15	2.68×10⁴	2.49×10⁴	6.68	74.06	0.921	0.743
11	5.76	2.95×10⁴	4.93×10⁴	10.09	47.66	0.940	0.599
7	5.55	8.79×10⁴	4.62×10⁴	9.89	94.34	0.935	0.838

Fig. 12 E-pH diagram for a amorphous Ni84.9Cr7.4Si4.2Fe3.5 alloy, b annealed sample

Fig. 13 Potentiostatic polarization test curves in the double-logarithmic scale carried out in 0.1 M NaOH and HCl solutions at 400 mV

Fig. 14 SEM images of the amorphous alloy and its annealed sample after potentiostatic polarization tests at 400 mV for 3600 s. a Amorphous alloy in 0.1 M NaOH; b annealed sample in 0.1 M NaOH; c amorphous alloy in 0.1 M HCl; d annealed sample in 0.1 M HCl

Fig. 15 XPS spectra of a Ni 2p, b O 1s recorded from the oxidation film formed on the amorphous alloy with Ar-ion sputtering for 60 s

Fig. 16 Element analysis of the solution after the potentiostatic polarization at 400 mV in a 0.1 M NaOH solution, b 0.1 M HCl solution

Fig. 17 EN spectra of a-d amorphous alloy, e-h its annealed sample in 0.1 M HCl

Table 5 Values of SI, IRMS, and LI after the potentiostatic tests of the amorphous Ni84.9Cr7.4Si4.2Fe3.5 alloy and its annealed sample in 0.1 M HCl at 400 mV for 3600 s

	Amorphous alloy	Annealed sample
Solution system	0.1 M HCl
S_I (nA)	0.19422	0.3784
I_RMS (nA)	0.19427	0.3785
LI	1	1

Fig. 18 Potential PSD curves of a amorphous alloy, b annealed sample after the potentiostatic test in 0.1 M HCl at 400 mV for 3600 s

Fig. 19 SKP 3D potential maps of a amorphous alloy, b its annealed sample

Fig. 20 Potential energy curves in the reaction of the amorphous alloy and its crystalline counterpart

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