Corrosion and Cavitation Erosion Behavior of GLNN/Cu Composite in Simulated Seawater

doi:10.11900/0412.1961.2021.00333

Acta Metall Sin

2022, Vol. 58

Issue (5): 599-609 DOI: 10.11900/0412.1961.2021.00333

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Corrosion and Cavitation Erosion Behavior of GLNN/Cu Composite in Simulated Seawater

PAN Chengcheng, ZHANG Xiang, YANG Fan, XIA Dahai(

), HE Chunnian, HU Wenbin(

)

Tianjin Key Laboratory of Composite and Functional Materials, School of Materials Science and Engineering, Tianjin University, Tianjin 300350, China

Cite this article:

PAN Chengcheng, ZHANG Xiang, YANG Fan, XIA Dahai, HE Chunnian, HU Wenbin. Corrosion and Cavitation Erosion Behavior of GLNN/Cu Composite in Simulated Seawater. Acta Metall Sin, 2022, 58(5): 599-609.

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Abstract

Herein, three-dimensional graphene-like nanosheet network (3D-GLNN)/copper (Cu) materials were synthesized using hop-pressing (HP) and hot-rolling (HR) methods and their corrosion resistance and mechanism were investigated using polarization curves, electrochemical impedance spectroscopy (EIS), and weight loss data after a cavitation corrosion test. Microstructural characterization results revealed that the 3D-GLNN structure was intact in the bulk composites, thereby restricting the effective grain growth of the Cu matrix. Compared with pure Cu, the Vickers hardness of 3D-GLNN/Cu fabricated using the HP and HR methods improved by 8% and 46%, respectively. Polarization curve results indicated that the anodic dissolution current of 3D-GLNN/Cu was considerably lower than that of pure Cu, indicating that 3D-GLNN/Cu exhibited better corrosion resistance. EIS measurements under a corrosion potential revealed that the electrode process kinetics was complex, with both charge and mass transfer controlling it. By extending the immersion time from 1 h to 9 d, the corrosion potential first became positive and then became negative. The capacitance arc at a high-frequency EIS range first increased and then decreased, attributed to the formation and detachment of a CuCl salt film. Diffusion impedance was observed in the low-frequency EIS range, with a phase angle of 18°-23°, indicating that the mass transfer process was not attributed to a single species but controlled by anodic and cathodic reactants. The constant phase angle element (CPE) behavior of the electrochemical system was further evaluated using the ohm-corrected phase angle and impedance modulus. The high-frequency phase angle was greater than -90 $°$ , while the slope of impedance modulus was approximately -0.9; thus, the CPE was used to model the EIS data. The CPE behavior was attributed to the surface distribution of the charge transfer resistance and interface capacitance, implying a time-constant dispersion on the surface. Weight loss data after the cavitation corrosion test indicated that pure Cu showed better cavitation resistance than 3D-GLNN/Cu fabricated using the HR and HP methods. This is because of the difference in the elastic modulus between the graphene and Cu matrix that caused deformation dissonance during cavitation erosion.

Key words: graphene composite corrosion EIS

Received: 11 August 2021

ZTFLH:

O646

Fund: National Natural Science Foundation of China(52031007);National Natural Science Foundation of China(52171077);Tianjin Science and Technology Support Project(17ZXCLGX00060);China Postdoctoral Science Foundation(2020M670648);China Postdoctoral Science Foundation(2021T140505)

About author: XIA Dahai, associate professor, Tel: 15222107261, E-mail: dahaixia@tju.edu.cnHU Wenbin, professor, Tel: 18202640829, E-mail: wbhu@tju.edu.cn

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	Chengcheng PAN
	Xiang ZHANG
	Fan YANG
	Dahai XIA
	Chunnian HE
	Wenbin HU

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https://www.ams.org.cn/EN/10.11900/0412.1961.2021.00333 OR https://www.ams.org.cn/EN/Y2022/V58/I5/599

Fig.1 Microstructure characterization of graphene network in 3D-GLNN/Cu composites, including SEM images of 3D-GLNN/Cu-HP (a, b) and 3D-GLNN/Cu-HR (c, d) after Cu etching in the surface, and TEM images of 3D-GLNN/Cu-HR after eliminating the Cu matrix (e, f) (GLNN—graphene-like nanosheet network, HP—hot pressing, HR—hot rolling)

Fig.2 OM images of hot-pressed pure Cu (a), 3D-GLNN/Cu-HP (b), and 3D-GLNN/Cu-HR (c, d) (70% reduction in thickness, RD—rolling direction, TD—transverse direction, ND—normal direction)

Fig.3 TEM images of the grain structure and interface of 3D-GLNN/Cu-HP (a-c) and 3D-GLNN/Cu-HR (d-f) (Arrows point to 3D-GLNN; GN—graphene)

Fig.4 Vickers hardnesses of hot-pressed pure Cu, 3D-GLNN/Cu-HP, and 3D-GLNN/Cu-HR

Fig.5 Polarization curve of 3D-GLNN/Cu composites in simulated seawater (E—potential, i—current density)

Table 1 Open circuit potential of Cu, 3D-GLNN/Cu-HP, and 3D-GLNN/Cu-HR in NaCl solutions for various immersion time up to 9 d

Fig.6 Nyquist (a, c, e) and Bode (b, d, f) plots of Cu and 3D-GLNN/Cu composite in simulated seawater for various immersion time up to 9 d
(a, b) Cu (c, d) 3D-GLNN/Cu-HP (e, f) 3D-GLNN/Cu-HR

Fig.7 Ohm resistance-corrected Bode plot for Cu and 3D-GLNN/Cu composites after immersing in NaCl solution for 1 h

Fig.8 Average mass loss of hot-pressed pure Cu, 3D-GLNN/Cu-HP, and 3D-GLNN/Cu-HR

Fig.9 Electrochemical equivalent circuit for Cu and 3D-GLNN/Cu composite in simulated seawater (C_d is interface capacitance, R_e is electrolyte resistance, $i d c$ is current flow through the pure capacitance, $i F a$ is anodic faradic current, $i F c$ is cathodic faradic current, $Z F a$ is anodic faradic impedance, $Z F c$ is cathodic faradic impedance, CPE_dc is constant phase element (representing interface capacitance), $R t a$ is the anodic charge transfer resistance, $R t c$ is cathodic charge transfer resistance, $Z θ, D a$ is impedance illustrating mass transport and partial blocking effect by CuCl, $Z D c$ is impedance illustrating O₂ mass transport)
(a) generalized model (b) detailed model

Sample	Time	$C e f f$ / (μF·cm^-2)	α	R_t / (kΩ·cm²)	$k c$ / (s^0.5·Ω^-1·cm^-2)
Cu	1 h	35.12	0.75	1.01	1.17 × 10^-4
	1 d	28.23	0.74	1.25	1.21 × 10^-4
	4 d	30.78	0.74	1.17	1.18 × 10^-4
3D-GLNN/Cu-HP	1 h	21.48	0.75	1.22	2.23 × 10^-4
	1 d	17.17	0.74	1.81	2.47 × 10^-4
	4 d	20.18	0.78	1.12	2.73 × 10^-4
3D-GLNN/Cu-HR	1 h	22.84	0.75	1.17	2.58 × 10^-4
	1 d	15.47	0.79	1.73	2.94 × 10^-4
	4 d	26.95	0.78	2.02	2.37 × 10^-4

Table 2 EIS fitting results using the electrochemical equivalent circuit

Fig.10 SEM images of hot pressed pure Cu (a-c), 3D-GLNN/Cu-HP (d-f), and 3D-GLNN/Cu-HR (g-i) (Figs.10c, f, and i are enlarged views of the highlighted regions in Figs.10b, e, and h)

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