Effect of Seawater Pressures on Microstructure Quantitative Analysis and Failure Dynamics Mechanism of Copper Alloys for Ship Propellers

doi:10.11900/0412.1961.2024.00279

Acta Metall Sin

2026, Vol. 62

Issue (9): 1591-1605 DOI: 10.11900/0412.1961.2024.00279

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Effect of Seawater Pressures on Microstructure Quantitative Analysis and Failure Dynamics Mechanism of Copper Alloys for Ship Propellers

YANG Huimin¹, LI Ruixue¹, ZHOU Chenxi¹, MA Yuxuan¹, ZHAO Xuhui¹, YONG Xingyue²(

), LIU Jingjun¹(

)

1 School of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
2 School of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Cite this article:

YANG Huimin, LI Ruixue, ZHOU Chenxi, MA Yuxuan, ZHAO Xuhui, YONG Xingyue, LIU Jingjun. Effect of Seawater Pressures on Microstructure Quantitative Analysis and Failure Dynamics Mechanism of Copper Alloys for Ship Propellers. Acta Metall Sin, 2026, 62(9): 1591-1605.

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Abstract

The microstructure evolution and stress-coupling failure of copper alloys are the primary factors contributing to their accelerated degradation in deep-sea environments, particularly under seawater pressure. In this study, high-manganese aluminum bronze (MAB), a material commonly used in ship propellers, is selected as the research subject. The atomic structure model of MAB alloy with aluminum atomic surface segregation and the strain-coupling model under varying seawater pressures are established through a combination of simulation and experimentation. The failure mechanism under different pressures is further examined, and the corrosion rate is predicted. As seawater pressure increases from 0.1 MPa to 10.0 MPa, the alloy's dislocation density and strain level progressively rise. When the pressure exceeds 6.0 MPa, these increases become more pronounced. The dislocation density of the alloy's (111) crystal surface increases by 6.08 × 10^-3 nm^-2, while the elastic micro-strain level rises by 0.79%. Experimental results indicate that the mass loss rate of copper alloys escalates with increasing pressure. Additionally, the morphology of the corrosion products transitions from a spot-like to a lamellar structure. Density functional theory calculations reveal that seawater pressure significantly affects the stability of the alloy structure. When seawater pressure surpasses the critical threshold of 6.0 MPa, the copper vacancy formation energy and migration-dissolution activation barrier decrease substantially, leading to a notable increase in the dissolution rate. The molecular dynamics method is employed to investigate the adsorption behavior of Cl^- on the alloy surface under deep-sea pressure and its influence on corrosion. The results demonstrate that increasing pressure enhances the chemical adsorption of Cl^-. However, at 10.0 MPa, the saturated adsorption of Cl^- on the surface does not significantly affect the dissolution rate.

Key words: copper alloy for ship propeller internal stress deep-sea pressure failure dynamics metal dissolution migration-dissolution barrier

Received: 14 August 2024

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	YANG Huimin
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	MA Yuxuan
	ZHAO Xuhui
	YONG Xingyue
	LIU Jingjun

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Fig.1 SEM image (a); EDS mappings of Cu (b), Al (c), Mn (d), Fe (e), and Ni (f); EDS spectrum (g) of manganese aluminum bronze (MAB) alloy; and schematics of atomic structure models of pure Cu (h), MAB alloy (i), and MAB-Al_seg alloy (j) (Inset in Fig.1g is EDS point result of MAB alloy elements. MAB-Al_seg alloy is an MAB alloy with partial substitution of surface Cu atoms by Al atoms)

Table 1 Total energy, binding energy, formation energy, and cohesive energy of pure Cu, MAB alloy, and MAB-Al_seg alloy models

Fig.2 Analyses of lattice structures and internal stresses of MAB (a-i) and MAB-Al_seg (j-l) alloys
(a) refined XRD pattern (R_p—profile R-factor, R_wp—weighted profile R-factor, X²—Chi-squared)
(b, c) microstrains (b) and dislocation densities (c) of different crystal planes
(d, e) HRTEM image (d) and the corresponding inverse fast Fouries transform (IFFT) image (e) (Inset in Fig.2e is corresponding fast Fouries transform (FFT) patterns, red circle repre-sents [111] crystal orientation)
(f) statistical diagram of (111) lattice space (d)
(g-i) strain/stress field maps in the x direction (g), y direction (h), and xy direction (i) (Rectangle areas refer to dipoles)
(j-l) radial distribution functions of surface (j), subsurface (k), and matrix (l) regions (g(r) is the relative density of atoms or molecules)

Fig.3 Processes of surface Cu atom migration-dissolution of MAB-Al_seg alloy (Black dotted circles represent Cu atomic vacancies. IS—initial state, VAC1—surface vacancy, TS—transition state, VAC2—subsurface vacancy, FS—final state (two-vacancy structure)) (a) and energy diagram of each step in the dynamic process of Cu atom migration-dissolution (b) in the MAB-Al_seg alloy (RDS—rate determining step, ΔE_vac1—vacancy formation energy of the surface Cu atom, ΔE_vac2—vacancy formation energy of the subsurface Cu atom)

Fig.4 Macroscopic corrosion morphologies of MAB alloy before and after corrosion for 10 h under different seawater pressures (a); SEM images of MAB alloys before corrosion (b) and after corrosion for 10 h under 0.1 MPa (c), 4.0 MPa (d), 6.0 MPa (e), 8.0 MPa (f), and 10.0 MPa (g) seawater pressures

Fig.5 Mass loss (a), area mass loss (b), corrosion rate (c), XRD pattern (d), microstrain level of (111) crystal plane (e), and dislocation density of (111) crystal plane (f) of MAB alloy after 10 h corrosion under different seawater pressures

Fig.6 Molecular dynamics simulation snapshot of the MAB-Al_seg alloy/seawater interface under seawater pressure (a); density distributions of H₂O molecules (b) and Cu²⁺ (c) on the MAB-Al_seg alloy surface under different seawater pressures; predictive model of Cu atom migration-dissolution on the surface of MAB-Al_seg alloy under seawater pressure (d); energy diagram of Cu atom migration-dissolution (e); dissolution rate constant (k) of Cu atoms (f); and schematics of the alloy surface dissolution process of hyperoxic zone (g) and hypoxic zone (h) (ads—intermediate corrosion products formed by adsorption of H₂O or OH^-)

Fig.7 Schematic of MAB-Al_seg alloy model with by Cl^- adsorption (a), adsorption energy at stable adsorption site (top of Al atom) on the surface of MAB-Al_seg alloy (b), binding energy (E_b) between Cl^- adsorption layer and matrix (c), work function of MAB-Al_seg alloy after Cl^- adsorption (d), energy diagram of Cu atom migration-dissolution processes of MAB-Al_seg alloy after Cl^- adsorption (e), and k of Cu atoms (f) at different seawater pressures

Fig.8 Adsorption model of different concentrations of Cl^- on the surface of MAB-Al_seg alloy (a), charge density distribution plots at different Cl^- concentration (b), binding energy between Cl^- adsorption layer and matrix (c), energy diagram of Cu atom migration-dissolution steps (d), and k of Cu atoms (e) at 10.0 MPa seawater pressure

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