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Journal of Chinese Society for Corrosion and protection  2024, Vol. 44 Issue (1): 167-174    DOI: 10.11902/1005.4537.2023.044
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Preparation and Anti-corrosion Properties of Silica Aerogel-modified Polyurethane Composite Coatings
LI Danhong, YANG Tengxun, SUN Tianxiang, LI Xinglinmao, MA Chengcheng, ZHANG Yue, CHEN Shougang()
School of Materials Science and Engineering, Ocean University of China, Qingdao 266100, China
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LI Danhong, YANG Tengxun, SUN Tianxiang, LI Xinglinmao, MA Chengcheng, ZHANG Yue, CHEN Shougang. Preparation and Anti-corrosion Properties of Silica Aerogel-modified Polyurethane Composite Coatings. Journal of Chinese Society for Corrosion and protection, 2024, 44(1): 167-174.

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Abstract  

Waterborne polyurethane (WPU) coating, a new kind of green material due to its excellent wear resistance, flexibility, low-temperature resistance and chemical medium resistance, has been widely attached attention to the field of marine corrosion protection. In this paper, hydrophilic modification of the hydrophobic silica (SiO2) aerogel was carried out by urea aldehyde modification. Then, the unmodified- and modified-SiO2 aerogels as filler were added into the WPU coatings with doses 0.5%, 1% and 2%, respectively, aiming to improve the anti-corrosion properties of WPU coatings. The functional groups and microstructure of SiO2 aerogel were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). These results proved that SiO2 aerogel was successfully modified by urea-formaldehyde. The anti-corrosion properties of coatings with different fillers were studied by contact angle test, electrochemical impedance spectroscopy (EIS), adhesion test and salt spray test. The results showed that the adhesion of the coating was significantly improved after adding hydrophilic-modified SiO2 aerogel. When 1% hydrophilic modified SiO2 aerogel was added, the adhesion of the composite coating was improved by 36% correspondingly, the low-frequency impedance modulus of the composite coating increased above 6 × 107 Ω·cm2 after immersion in 3.5% NaCl solution for 70 d. There was no obvious bubbling phenomenon on the surface of the composite coating with 1% hydrophilic modified SiO2 aerogel after the 480 h salt spray testing, which showed its best anti-corrosion performance. Thus, it is concluded that the hydrophilic modification of the hydrophobic SiO2 aerogel by the urea aldehyde modification can improve the dispersibility of the hydrophobic SiO2 aerogel in the WPU coating, the interface compatibility with the coating and the barrier and shielding effect of the SiO2 aerogel on corrosive ions. Furthermore, the corrosion resistance of the WPU coating is improved.
Key words:  silicon dioxide aerogel      waterborne polyurethane      hydrophilic modification      anti-corrosion property      long-term anticorrosion     
Received:  22 February 2023      32134.14.1005.4537.2023.044
ZTFLH:  TG174  
Fund: National Natural Science Foundation of China(52371081)
Corresponding Authors:  CHEN Shougang, E-mail: sgchen@ouc.edu.cn
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LI Danhong
YANG Tengxun
SUN Tianxiang
LI Xinglinmao
MA Chengcheng
ZHANG Yue
CHEN Shougang

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https://www.jcscp.org/EN/10.11902/1005.4537.2023.044     OR     https://www.jcscp.org/EN/Y2024/V44/I1/167

Fig.1  FTIR spectra of silica aerogel before and after modification
Fig.2  SEM image of SiO2 aerogel, elemental map scannings of C, Si and O, and EDS spectrum
Fig.3  Contact angles of polyurethane composite coatings containing unmodified and modified SiO2 aerogels
Fig.4  Comparison of adhesions of polyurethane composite coatings containing unmodified and modified SiO2 aerogels
Fig.5  Nyquist (a), impedance module (b) and phase angle (c) plots of EIS curves of blank polyurethane coating
Fig.6  Nyquist (a), impedance module (b) and phase angle (c) plots of EIS curves of polyurethane composite coatings containing different mass ratios of unmodified SiO2 aerogel (1, 2 and 3 represent the coatings containing 0.5%, 1% and 2% unmodified SiO2 aerogel, respectively)
Fig.7  Nyquist (a), module (b) and phase (c) plots of EIS curves of polyurethane composite coatings containing different mass ratios of modified SiO2 aerogel (1, 2 and 3 represent the coatings containing 0.5%, 1% and 2% modified SiO2 aerogel, respectively)
Fig.8  Equivalent circuit for fitting EIS of various coatings
Sample

Rc

Ω·cm2

CPE c

Cc

F·cm-2

Rct

Ω·cm2

CPEdl

Cdl

F·cm-2

Yc / F·cm-2·S n-1ncYdl / F·cm-2·S n-1ndl
01.19 × 1032.82 × 10-70.753.09 × 10-88.89 × 1037.50 × 10-240.021.29 × 10-27
1% SiO28.16 × 1048.84 × 10-90.957.35 × 10-92.06 × 1066.87 × 10-80.522.1 × 10-8
1% SiO2 M1.63 × 1071.05 × 10-90.991.05 × 10-94.29 × 1075.95 × 10-90.655.11 × 10-9
Table 1  Fitting parameters of EIS curves of various coatings after immersion for 70 d
Fig.9  Macro-morphologies of various as-prepared polyurethane composite coatings after salt spray test for 0-20 d
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