Photothermal and pH dual-responsive self-healing coating for smart corrosion protection

doi:10.1016/j.jmst.2021.08.044

Abstract

Abstract:

A novel self-healing coating with photothermal and pH dual-responsive properties has been designed to protect carbon steel against corrosion by loading the stimuli-responsive microcapsules into a shape memory epoxy coating. The sandwich-like microcapsules were based on reduced graphene oxide/mesoporous silica (rGO@MS) assembled with a pH-responsive poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) layer, and were loaded with benzotriazole (BTA) inhibitors (abbreviated as rGO@MS-P-BTA). Under near-infrared (NIR) light irradiation, the prominent photothermal effect of rGO could not only elevate the coating temperature to activate the shape memory effect and close the coating scratch, but also facilitate the release of corrosion inhibitors to suppress the corrosion activity. Moreover, the PDMAEMA as a pH-driven “gatekeeper” realized the controlled release of BTA from microcapsules at acid conditions. The surface morphology analysis, electrochemical impedance spectroscopy (EIS), and scanning electrochemical microscopy (SECM) were performed to evaluate the self-healing performance of the composite coatings. The results showed that the combination of NIR light and pH-responsive self-healing effects endowed the coating with short healing time and prominent healing efficiency.

Key words: Self-healing coatings, Corrosion inhibitors, Photothermal effects, pH-responsive, Shape memory polymers

Yao Huang, Panjun Wang, Weimin Tan, Wenkui Hao, Lingwei Ma, Jinke Wang, Tong Liu, Fan Zhang, Chenhao Ren, Wei Liu, Dawei Zhang. Photothermal and pH dual-responsive self-healing coating for smart corrosion protection[J]. J. Mater. Sci. Technol., 2022, 107: 34-42.

Figures/Tables 10

Scheme 1. The preparation process of rGO@MS-P-BTA.

Fig. 1. TEM images of (a) (b) rGO@MS and (c) (d) rGO@MS-P.

Fig. 2. (a) Zeta potential of the rGO@MS, PDMAEMA and rGO@MS-P; (b) FTIR spectra of the rGO@MS, PDMAEMA, rGO@MS-P, rGO@MS-P-BTA and BTA.

Fig. 3. (a) N2 adsorption-desorption isotherms of rGO@MS and rGO@MS-P; (b) the pore size distribution curves of rGO@MS and rGO@MS-P.

Fig. 4. (a) Standard curves of BTA at pH= 3, 7, 11, obtained from the corresponding UV-Vis spectra; (b) Release of BTA from rGO@MS-P-BTA at different pH values; (c) release of BTA in 3.5 wt.% NaCl solution with or without NIR irradiation (808 nm, 3 W/cm2).

Fig. 5. (a) DSC curves of epoxy coatings with different rGO@MS-P-BTA microcapsules contents of 0 wt.%, 0.5 wt.%, 1 wt.%, 2 wt.%; (b) Surface temperature and photothermal behavior of the coating containing 0 wt.%, 0.5 wt.%, 1 wt.%, 2 wt.% rGO@MS-P-BTA microcapsules at NIR laser exposure for 15 s (808 nm, 3 W/cm2); (c) SEM images of healed coatings containing 0 wt.%, 0.5 wt.%, 1 wt.%, 2 wt.% rGO@MS-P-BTA microcapsules.

Fig. 6. Bode and phase angle plots of (a) scratched epoxy coating; (b) healed coating containing 0.5 wt.% rGO@MS-P-BTA; (c) healed coating containing 1 wt.% rGO@MS-P-BTA; (d) healed coating containing 2 wt.% rGO@MS-P-BTA; (e) healed coating containing 1 wt.% rGO@MS-P; (f) variation trend of low frequency impedance.

Fig. 7. (a, b) Equivalent electric circuits of coatings in 3.5 wt.% NaCl solution; (c) The variation trend of charge transfer resistance.

Fig. 8. (a) SECM maps of the scratched pure epoxy coating immersed in a 0.1 mol/L NaCl solution for 1 h, 4 h and 8 h; (b) SECM maps of the scratched epoxy coating containing 1 wt.% rGO@MS-P-BTA microcapsules immersed in a 0.1 mol/L NaCl solution for 1 h, 4 h and 8 h; (c) SECM maps of the healed epoxy coating containing 1 wt.% rGO@MS-P microcapsules immersed in a 0.1 mol/L NaCl solution for 1 h, 4 h and 8 h; (d) SECM maps of the healed epoxy coating containing 1 wt.% rGO@MS-P-BTA microcapsules immersed in a 0.1 mol/L NaCl solution for 1 h, 4 h and 8 h.

Fig. 9. Schematic illustration of self-healing coating doped with rGO@MS-P-BTA microcapsules.

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