Durable self-polishing antifouling Cu-Ti coating by a micron-scale Cu/Ti laminated microstructure design

doi:10.1016/j.jmst.2020.11.038

Abstract

Abstract:

Marine biofouling is a major issue deteriorating the service performance and lifespan of marine infrastructures. The development of a durable, long-term, and environment-friendly antifouling coating is therefore of significant importance but still a critical challenge in maritime engineering. Herein, we developed a Cu-Ti composite antifouling coating with micron-sized alternating laminated-structure of Cu/Ti by plasma spraying of mechanically mixed Cu/Ti powders. The coating was designed to enable controlled release of Cu ions through galvanic dissolution of Cu laminates from the Cu/Ti micro-galvanic cell in aqueous solution. Results showed that remarkable antifouling efficiency against bacterial survival and adhesion up to ~100 % was achieved for the Cu-Ti coating. Cu/Ti micro-galvanic cell was in-situ formed within Cu-Ti coating and responsible for its Cu ions release. The successive dissolution of Cu laminates resulted in the formation of micro-channels under Ti laminates near surface, which contributed to controlled slow Cu ions release and self-polishing effect. Thus, environment-friendly antifouling capability and ∼200 % longer antifouling lifetime than that of the conventional organic antifouling coatings can be achieved for the Cu-Ti coating. On the other hand, as compared to the conventional organic antifouling coatings, the Cu-Ti composite coating presented much higher mechanical durability due to its strong adhesion strength, excellent mechanical properties, and two orders lower wear rate. The present laminated Cu-Ti coating exhibits combination of outstanding antifouling performance and high mechanical durability, which makes this coating very potentially candidates in marine antifouling application.

Key words: Marine antifouling, Cu-Ti coating, Plasma spraying, Micro-galvanic dissolution, Durable, Self-polishing

Jiajia Tian, Kangwei Xu, Junhua Hu, Shijie Zhang, Guoqin Cao, Guosheng Shao. Durable self-polishing antifouling Cu-Ti coating by a micron-scale Cu/Ti laminated microstructure design[J]. J. Mater. Sci. Technol., 2021, 79: 62-74.

Figures/Tables 12

Fig. 1. (a) Cross-sectional microstructure of the Cu-Ti composite coating. (b) Higher magnification image showing the Cu and Ti laminates. (c) EDS linear scan result across Cu/Ti/Cu laminates taking from the area as marked with L1 in (b). (d) XRD patterns of the Cu-Ti coating and the raw Cu and Ti powder.

Fig. 2. SKPFM result of the Cu-Ti composite coating: (a) topography map; (b) Volta potential map; and (c) line-profile result of the relative Volta potential along the L1 marked in (b).

Fig. 3. Release profile of Cu ions as a function of immersion period for Cu-Ti composite coating: (a) release rate of Cu ions and (b) cumulative Cu release.

Fig. 4. Antifouling performance of different samples. Digital photos of E. coli colonies Petri dish after incubated in E. coli-containing media for 8 h for: (a) blank control sample; (b) bare TC4 substrate; and (c) Cu-Ti composite coating. (d) The antibacterial coefficient results for different samples. The adherence behavior of Bacillus sp. bacteria on (e) TC4 substrate and (f) Cu-Ti coating after incubated in Bacillus sp. bacteria-containing media for 48 h.

Fig. 5. The surface morphology and the corresponding EDS mapping results of Cu-Ti coating after being immersed in artificial seawater for different periods: (a), (c) and (e) surface morphology images taken at lower magnification; (b), (d) and (f) surface morphology images taken at higher magnification.

Fig. 6. The cross-sectional microstructure of the Cu-Ti coating after being immersed into artificial seawater for different periods: (a) 7 days; (b) 30 days; and (c-f) 240 days. (d) A higher magnification image of the top region in (c). (e) A higher magnification image of the dissolving Cu region in (d). (f) Ti laminates left after Cu laminates dissolved.

Fig. 7. The adhesion strengths (a) and hardness and elastic modulus (b) of the Cu-Ti coating and CO-SPC coating.

Table 1 Mechanical properties of the Cu-Ti coating and the CO-SPC coating.

Materials	H (GPa)	E (GPa)	H/E	H³/E² (GPa)
CO-SPC coating	0.04	2.7	0.015	8.8 × 10 ^-6
Cu-Ti coating	3.1	125.8	0.024	1.8 × 10 ^-3

Fig. 8. Wear behavior of the Cu-Ti coating and CO-SPC coating: (a) friction coefficient; (b) wear rate; (c) 3D optical profilometer images showing the wear tracks of the two coatings; and (d) a typical line profile of the wear tracks.

Fig. 9. SEM images showing the worn surfaces of (a-c) CO-SPC coating and (d-f) Cu-Ti composite coating at different magnifications. (c) A magnified image showing the exposed substrate in (b). (f) A magnified image of the tribolayer in (e).

Table 2 Main chemical composition of the worn surface characterized by EDS.

Points	Chemical composition (wt.%)
	Ti	Cu	O	C	Al	V
1	86.14	-	3.1	-	6.21	4.54
2	13.67	-	20.04	66.58	-	-
3	30.69	62.82	6.49	-	-	-
4	85.28	6.95	7.78	-	-	-

Fig. 10. Illustration of the antifouling mechanism of the Cu-Ti composite coating.

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