Acta Metallurgica Sinica (English Letters) ›› 2023, Vol. 36 ›› Issue (11): 1893-1908.DOI: 10.1007/s40195-023-01600-0
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Izuchukwu K. Nwokolo1,2, Hongwei Shi1,2,3(
), Paul C. Uzoma4, Sharjeel Ahmed1,2, Jiwen Li1,2, Fuchun Liu1,2,5()
Received:2023-05-14
Revised:2023-06-30
Accepted:2023-07-23
Online:2023-11-10
Published:2023-09-19
Contact:
Hongwei Shi, hwshi@imr.ac.cn;
Fuchun Liu, fcliu@imr.ac.cn
Izuchukwu K. Nwokolo, Hongwei Shi, Paul C. Uzoma, Sharjeel Ahmed, Jiwen Li, Fuchun Liu. Protective Coatings Containing ZnMOF-BTA Metal-Organic Framework for Active Protection of AA2024-T3[J]. Acta Metallurgica Sinica (English Letters), 2023, 36(11): 1893-1908.
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Fig. 1 a Synthetic procedure of ZnMOF-BTA; b XRD patterns of BTA, H2TDC, Zn (NO3)2·6H2O, and ZnMOF-BTA; c FT-IR plots of BTA, H2TDC, and ZnMOF-BTA
Fig. 2 a SEM morphology, b EDS spectrum, c XPS spectrum, d TGA-DTA curves of ZnMOF-BTA crystals
Fig. 3 SEM images and the corresponding EDS spectra of polished AA2024-T3 surface a before immersion, b after 72 h immersion in 3.5 wt% NaCl solution, c after 72 h immersion in extract solution of 2 wt% ZnMOF-BTA at room temperature
Fig. 4 Polarization curves of polished AA2024-T3 panels immersed in 3.5 wt% NaCl and extract solutions of ZnMOF-BTA particles at room temperature
| Sample | Ecorr (V) | Icorr (Am/cm2) | I.E (%) |
|---|---|---|---|
| Blank NaCl solution | − 0.490 | 2.64 × 10−6 | - |
| 2 wt% ZnMOF-BTA extract solution | − 0.468 | 6.33 × 10−7 | 76.02 |
| 4 wt% ZnMOF-BTA extract solution | − 0.173 | 9.50 × 10−8 | 96.40 |
| 6 wt% ZnMOF-BTA extract solution | − 0.056 | 5.00 × 10−9 | 99.81 |
Table 1 Fitting results of polarization curves of the polished AA2024-T3 panels immersed in 3.5 wt% NaCl and extract solutions of ZnMOF-BTA particles at room temperature
| Sample | Ecorr (V) | Icorr (Am/cm2) | I.E (%) |
|---|---|---|---|
| Blank NaCl solution | − 0.490 | 2.64 × 10−6 | - |
| 2 wt% ZnMOF-BTA extract solution | − 0.468 | 6.33 × 10−7 | 76.02 |
| 4 wt% ZnMOF-BTA extract solution | − 0.173 | 9.50 × 10−8 | 96.40 |
| 6 wt% ZnMOF-BTA extract solution | − 0.056 | 5.00 × 10−9 | 99.81 |
Fig. 5 Morphologies of a cross-section of a sample coated with polyurethane coating only b sample coated with a polyurethane coating containing ZnMOF-BTA particles
Fig. 6 Bode plots of the behavior of coatings without and with ZnMOF-BTA particles on AA 2024-T3 immersed in 3.5 wt% NaCl solution. a Blank coating without ZnMOF-BTA particles, b coating with 2 wt% ZnMOF-BTA particles, c coating with 5 wt% ZnMOF-BTA particles, d coating with 10 wt% ZnMOF-BTA particles, e the evolution of low-frequency impedance values
Fig. 7 Equivalent circuit models used in fitting the EIS data of coated samples during immersion in 3.5 wt% NaCl solution
| Sample | Time (h) | CPEc | Rpo (Ω cm2) | CPEdl | Rp (Ω cm2) | W | χ2 | ||
|---|---|---|---|---|---|---|---|---|---|
| Yc (S cm−2 sn) | nc | Ydl (S cm−2 sn) | ndl | ||||||
| Blank | 6 | 1.97 × 10−9 | 0.89 | 1.12 × 108 | - | - | - | - | 1.35 × 10−2 |
| 48 | 5.82 × 10−8 | 0.95 | 1.87 × 107 | 8.97 × 10−10 | 0.95 | 1.37 × 108 | - | 4.17 × 10−3 | |
| 144 | 1.29 × 10−7 | 0.75 | 1.15 × 104 | 6.53 × 10−7 | 0.99 | 5.23 × 106 | - | 5.46 × 10−3 | |
| 360 | 9.71 × 10−8 | 0.78 | 7.43 × 104 | 6.19 × 10−8 | 0.95 | 6.87 × 105 | - | 2.75 × 10−3 | |
| 720 | 1.85 × 10−7 | 0.66 | 1.39 × 104 | 3.77 × 10−7 | 0.98 | 6.99 × 104 | - | 5.40 × 10−3 | |
| 1440 | 1.29 × 10−7 | 0.75 | 1.15 × 104 | 6.53 × 10−7 | 0.99 | 5.23 × 104 | - | 5.46 × 10−3 | |
| 2 wt% | 6 | 1.60 × 10−9 | 0.88 | 4.84 × 107 | - | - | - | - | 6.49 × 10−3 |
| 48 | 5.74 × 10−10 | 0.94 | 3.98 × 1010 | - | - | - | - | 2.28 × 10−3 | |
| 144 | 5.70 × 10−11 | 0.80 | 1.00 × 108 | - | - | - | - | 8.02 × 10−3 | |
| 360 | 5.14 × 10−10 | 0.95 | 1.17 × 109 | 2.08 × 10−9 | 0.79 | 8.95 × 1010 | 1.23 × 10−9 | 7.55 × 10−4 | |
| 720 | 9.29 × 10−9 | 0.71 | 2.01 × 107 | 7.36 × 10−6 | 0.78 | 4.15 × 10−2 | 8.71 × 10−15 | 1.53 × 10−2 | |
| 1440 | 1.24 × 10−8 | 0.71 | 2.19 × 105 | 1.03 × 10−7 | 0.98 | 1.00 × 10−2 | 2.26 × 10−4 | 6.39 × 10−3 | |
| 5 wt% | 6 | 1.62 × 10−9 | 0.89 | 3.64 × 107 | - | - | - | - | 2.93 × 10−3 |
| 48 | 1.23 × 10−11 | 0.88 | 5.09 × 108 | - | - | - | - | 1.44 × 10−2 | |
| 144 | 7.40 × 10−11 | 0.93 | 1.82 × 1010 | - | - | - | - | 1.52 × 10−2 | |
| 360 | 7.05 × 10−12 | 0.92 | 1.86 × 1010 | - | - | - | - | 1.21 × 10−2 | |
| 720 | 5.05 × 10−10 | 0.96 | 2.06 × 107 | 6.81 × 10−10 | 0.92 | 6.67 × 109 | 1.10 × 10−9 | 1.05 × 10−3 | |
| 1440 | 5.25 × 10−10 | 0.95 | 2.24 × 107 | 7.40 × 10−10 | 0.97 | 2.13 × 108 | 3.13 × 10−7 | 2.18 × 10−3 | |
| 10 wt% | 1.44 × 10−10 | 0.89 | 5.74 × 107 | - | - | - | - | 5.19 × 10−3 | |
| 48 | 8.33 × 10−12 | 0.91 | 4.06 × 109 | - | - | - | - | 2.03 × 10−2 | |
| 144 | 6.86 × 10−11 | 0.93 | 1.59 × 1010 | - | - | - | - | 9.95 × 10−3 | |
| 360 | 6.86 × 10−12 | 0.92 | 2.91 × 1010 | - | - | - | - | 1.54 × 10−2 | |
| 720 | 6.86 × 10−11 | 0.93 | 1.90 × 1010 | - | - | - | - | 9.76 × 10−3 | |
| 1440 | 6.90 × 10−11 | 0.93 | 1.76 × 1010 | - | - | - | - | 7.79 × 10−3 | |
Table 2 Equivalent circuit parameters extracted from EIS data of the coated samples immersed in 3.5 wt% NaCl solution for 1440 h
| Sample | Time (h) | CPEc | Rpo (Ω cm2) | CPEdl | Rp (Ω cm2) | W | χ2 | ||
|---|---|---|---|---|---|---|---|---|---|
| Yc (S cm−2 sn) | nc | Ydl (S cm−2 sn) | ndl | ||||||
| Blank | 6 | 1.97 × 10−9 | 0.89 | 1.12 × 108 | - | - | - | - | 1.35 × 10−2 |
| 48 | 5.82 × 10−8 | 0.95 | 1.87 × 107 | 8.97 × 10−10 | 0.95 | 1.37 × 108 | - | 4.17 × 10−3 | |
| 144 | 1.29 × 10−7 | 0.75 | 1.15 × 104 | 6.53 × 10−7 | 0.99 | 5.23 × 106 | - | 5.46 × 10−3 | |
| 360 | 9.71 × 10−8 | 0.78 | 7.43 × 104 | 6.19 × 10−8 | 0.95 | 6.87 × 105 | - | 2.75 × 10−3 | |
| 720 | 1.85 × 10−7 | 0.66 | 1.39 × 104 | 3.77 × 10−7 | 0.98 | 6.99 × 104 | - | 5.40 × 10−3 | |
| 1440 | 1.29 × 10−7 | 0.75 | 1.15 × 104 | 6.53 × 10−7 | 0.99 | 5.23 × 104 | - | 5.46 × 10−3 | |
| 2 wt% | 6 | 1.60 × 10−9 | 0.88 | 4.84 × 107 | - | - | - | - | 6.49 × 10−3 |
| 48 | 5.74 × 10−10 | 0.94 | 3.98 × 1010 | - | - | - | - | 2.28 × 10−3 | |
| 144 | 5.70 × 10−11 | 0.80 | 1.00 × 108 | - | - | - | - | 8.02 × 10−3 | |
| 360 | 5.14 × 10−10 | 0.95 | 1.17 × 109 | 2.08 × 10−9 | 0.79 | 8.95 × 1010 | 1.23 × 10−9 | 7.55 × 10−4 | |
| 720 | 9.29 × 10−9 | 0.71 | 2.01 × 107 | 7.36 × 10−6 | 0.78 | 4.15 × 10−2 | 8.71 × 10−15 | 1.53 × 10−2 | |
| 1440 | 1.24 × 10−8 | 0.71 | 2.19 × 105 | 1.03 × 10−7 | 0.98 | 1.00 × 10−2 | 2.26 × 10−4 | 6.39 × 10−3 | |
| 5 wt% | 6 | 1.62 × 10−9 | 0.89 | 3.64 × 107 | - | - | - | - | 2.93 × 10−3 |
| 48 | 1.23 × 10−11 | 0.88 | 5.09 × 108 | - | - | - | - | 1.44 × 10−2 | |
| 144 | 7.40 × 10−11 | 0.93 | 1.82 × 1010 | - | - | - | - | 1.52 × 10−2 | |
| 360 | 7.05 × 10−12 | 0.92 | 1.86 × 1010 | - | - | - | - | 1.21 × 10−2 | |
| 720 | 5.05 × 10−10 | 0.96 | 2.06 × 107 | 6.81 × 10−10 | 0.92 | 6.67 × 109 | 1.10 × 10−9 | 1.05 × 10−3 | |
| 1440 | 5.25 × 10−10 | 0.95 | 2.24 × 107 | 7.40 × 10−10 | 0.97 | 2.13 × 108 | 3.13 × 10−7 | 2.18 × 10−3 | |
| 10 wt% | 1.44 × 10−10 | 0.89 | 5.74 × 107 | - | - | - | - | 5.19 × 10−3 | |
| 48 | 8.33 × 10−12 | 0.91 | 4.06 × 109 | - | - | - | - | 2.03 × 10−2 | |
| 144 | 6.86 × 10−11 | 0.93 | 1.59 × 1010 | - | - | - | - | 9.95 × 10−3 | |
| 360 | 6.86 × 10−12 | 0.92 | 2.91 × 1010 | - | - | - | - | 1.54 × 10−2 | |
| 720 | 6.86 × 10−11 | 0.93 | 1.90 × 1010 | - | - | - | - | 9.76 × 10−3 | |
| 1440 | 6.90 × 10−11 | 0.93 | 1.76 × 1010 | - | - | - | - | 7.79 × 10−3 | |
Fig. 8 Photos of coated samples after 30 days of exposure to 5 wt% NaCl solution
Fig. 9 Inhibition mechanism of polyurethane coating containing ZnMOF-BTA particles
Fig. 10 a Cross-cut test and b impact test micrograph of polyurethane coating containing ZnMOF-BTA particles
Fig. 11 SEM micrographs of coated samples (insets are photos of water droplets on each coating)
Fig. 12 AFM images showing the surface roughness of polyurethane coatings containing a 0 wt% (blank), b 2 wt%, c 5 wt%, d 10 wt% ZnMOF-BTA particles
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