Effect of Soaking Time on Properties of Molybdate Conversion Film of B10 Cu⁃Ni Alloy

doi:10.12422/j.issn.1672-6952.2024.02.009

Abstract

Abstract:

Copper nickel alloys have excellent corrosion resistance and mechanical properties, therefore it is widely used in marine engineering. However, due to its complex service environment, copper nickel alloys are prone to corrosion and leakage, resulting in irreversible losses. A corrosion?resistant conversion film was prepared on the surface of copper nickel alloy to improve its corrosion resistance performance; Electrochemical impedance, Tafel polarization curve, scanning electron microscopy, and energy spectrum analysis were performed, and the surface covered corrosion products of the conversion film were observed by X?ray photoelectron spectroscopy (XPS). The results showed that when the B10 copper nickel alloy sample was immersed in a solution containing molybdate for 120 minutes, the solution transfer resistance (R_ct) and membrane resistance (R_p) reached their peak values, and the corrosion inhibition rate was as high as 92.5%; the conversion film contains copper and nickel oxides as well as hydroxides, while molybdenum exists in the form of +4 and +6 valence oxides.

Key words: B10 Cu?Ni alloy, Oxidation film, Molybdate, Corrosion

摘要：

B10铜镍合金具有优异的耐蚀性能和力学性能，因此被广泛应用于海洋工程。但是，由于其服役环境复杂，B10铜镍合金易发生腐蚀而导致泄漏，造成不可挽回的损失。制备了B10铜镍合金表面防腐转化膜，以提高合金表面的耐蚀性能；进行了电化学阻抗、塔菲尔极化曲线（Tafel极化曲线）、扫描电镜与能谱分析，并通过X射线光电子谱（XPS）观察了转化膜的表面覆盖腐蚀产物。结果表明，当B10铜镍合金试样在含钼酸盐的溶液中浸泡120 min时，溶液转移电阻（R_ct）和膜电阻（R_p）达到峰值，且缓蚀率高达92.5%；转化膜中含有Cu和Ni的氧化物以及氢氧化物，Mo以+4价和+6价氧化物的形式存在于转化膜中。

关键词: B10铜镍合金, 氧化膜, 钼酸盐, 腐蚀

CLC Number:

TE980.45

Nianchu WU, Yue LI, Rui WANG. Effect of Soaking Time on Properties of Molybdate Conversion Film of B10 Cu⁃Ni Alloy[J]. Journal of Liaoning Petrochemical University, 2024, 44(2): 55-62.

吴念初, 李月, 王蕤. 浸泡时间对B10铜镍合金钼酸盐转化膜性能的影响[J]. 辽宁石油化工大学学报, 2024, 44(2): 55-62.

Figures/Tables 14

Table 1 Chemical composition of B10 copper nickel alloy

组分	w/%	组分	w/%
Ni	10.550 0	P	0.004 0
Fe	1.760 0	C	0.010 0
Mn	0.800 0	Pb	<0.005 0
Zn	0.031 0	Cu	余量
S	0.004 1

Fig.1 Electrochemical impedance spectrum after immersion in B10

Fig.2 Equivalent circuit diagram for impedance data fitting

Table 2 Electrochemical impedance fitting data of the conversion membrane after immersion

时间/min	R_s/(Ω·cm²)	Y_0,CPE1/(Ω^-1·cm^-2·S ⁿ )	n₁	R_ct/(kΩ·cm²)	Y_0,CPE2/(Ω^-1·cm^-2·S ⁿ )	n₂	R_f/(kΩ·cm²)
0	5.06	8.63×10^-4	0.81	0.649	—	—	—
30	4.55	3.87×10^-5	0.87	1.040	9.53×10^-5	0.58	116.0
60	5.11	4.73×10^-5	0.86	0.991	3.94×10^-4	0.55	76.6
120	4.93	5.35×10^-5	0.90	4.011	7.63×10^-5	0.58	134.0
180	4.66	5.46×10^-5	0.85	1.441	1.39×10^-4	0.55	84.2
240	5.07	7.32×10^-5	0.83	0.854	3.22×10^-4	0.57	63.2

Fig.3 Polarization curve of B10 copper nickel alloy with surface conversion film in 3.5% NaCl solution

Table 3 Fitting parameters of Tafel polarization curve

时间/min	E_corr/ V	I_corr/ (A·cm^－2)	η/%
0	－0.308	2.02×10^-5	—
30	－0.279	1.17×10^-5	42.3
60	-0.258	1.19×10^-5	41.3
120	-0.285	1.52×10^-6	92.5
180	-0.311	2.11×10^-6	89.6
240	-0.303	1.84×10^-6	90.9

Fig.4 Relationship between linear polarization resistance and soaking time

Fig.5 Surface morphology of blank sample and chemical conversion film

Fig.6 Energy spectrum analysis results of the sample surface after soaking for 120 minutes

Table 4 The mass fraction of each element in the conversion film obtained through energy spectrum analysis

元素	w/%	误差率/%
总计	100.00
C	6.12	0.20
O	2.75	0.07
Si	0.33	0.04
P	0.18	0.05
Mn	0.88	0.08
Fe	2.05	0.09
Ni	10.91	0.18
Cu	64.23	0.32
Mo	0.62	0.17
Au	11.93	0.27

Fig.7 High resolution Cu 2p spectrum

Fig.8 High resolution Ni 2p spectrum

Fig.9 High resolution Mo 3d spectrum

Fig.10 High resolution O 1s spectrum

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