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Journal of Chinese Society for Corrosion and protection  2016, Vol. 36 Issue (1): 59-66    DOI: 10.11902/1005.4537.2015.023
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Preparation and Corrosion Resistance of PANI/TiO2/Epoxy Coatings
Shan ZHANG1,Lina ZHOU2,Lu JIAN1,Xu WANG1()
1. School of Materials Science and Engineering, Southwest Petroleum University, Chengdu 610500, China
2. School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China
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Abstract  

Polyaniline/TiO2 nano composites with different weight ratios of polyaniline to TiO2 were synthesized using chemical oxidative polymerization through polymerizing polyaniline (PANI) onto the nano TiO2 surface. The prepared PANI/TiO2 composites were characterized by FTIR, XRD and SEM. Then PANI/TiO2/epoxy resin coating was prepared by blending epoxy resin with polyaniline/TiO2 nano powders, while coating formulation with excellent mechanical performance was acquired through orthogonal experiments and trial corrosion tests. The corrosion performance of X70 steel coated with the optimal coating was examined in S2- and Cl- containing solutions at different temperatures. The results show that there exists strong interaction between the nano TiO2 particle and PANI within the PANI/TiO2 composites. Many factors could affect the mechanical property of the coatings, according to their impact degree, which may be ranked as the following sequence: PANI>TiO2>curing temperature>solvent content>solvent ratio. The optimal PANI/TiO2/epoxy resin coating with excellent mechanical properties and corrosion performance could be acquired by an optimal process with the following parameters: the mass ratio of PANI to epoxy resin is 1 to 100; TiO2 to epoxy resin is 1 to 100; curing at 60 ℃. The content of solvent to epoxy resin is 5 to 10 and NMP/n-butanol=2/1(solvent molar ratio). Furthermore, at 72 h after immersion of the optimal coating in 3.5%NaCl solution at 65 ℃, a maximum appeared on its impedance vs time curve, whilst the coating keeps an excellent corrosion resistance even after immersion in 3%Na2S solution for 120 h at 80 ℃.
Key words:  PANI/TiO2/epoxy coating      preparation      corrosion resistance     
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Shan ZHANG
Lina ZHOU
Lu JIAN
Xu WANG

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Shan ZHANG,Lina ZHOU,Lu JIAN,Xu WANG. Preparation and Corrosion Resistance of PANI/TiO2/Epoxy Coatings. Journal of Chinese Society for Corrosion and protection, 2016, 36(1): 59-66.

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https://www.jcscp.org/EN/10.11902/1005.4537.2015.023     OR     https://www.jcscp.org/EN/Y2016/V36/I1/59

Level PANI / g[A] TiO2 / g[B] NMP+N-butanol/ g [C] NMP/N-butanol(molar ratio) [D] Curing temperature / ℃ [E]
1 0.05 0 3 1:1 60
2 0.1 0.1 4 2:1 80
3 0.15 0.2 5 1:2 100
4 0.2 0.3 6 3:1 120
Table 1  Factors and levels of the orthogonal test
Fig.1  FTIR spectra of PANI and PANI/TiO2
Fig.2  SEM images of TiO2 (a) and PANI/TiO2 (b)
Flexibilitycrack Score Pencil Hardness
H		 Score Impact Resistance / cm Score Adhesion level Score
No 100 6H 100 50 100 1 100
Slight 66.7 5H 91.66 40 80 2 85.71
Obvious 33.3 4H 83.33 30 60 3 71.42
3H 75 20 40 4 57.14
2H 66.67 5~20 5 5 42.85
1H 58.33 <5 0 6 28.57
7 14.28
Table 2  Standard of multi-index score
Test A B C D E Score
1 A1 B1 C1 D1 E1 75.47
2 A1 B2 C2 D2 E2 93.33
3 A1 B3 C3 D3 E3 90.67
4 A1 B4 C4 D4 E4 72.14
5 A2 B1 C2 D3 E4 90
6 A2 B2 C1 D4 E3 95
7 A2 B3 C4 D1 E2 97.5
8 A2 B4 C3 D2 E1 100
9 A3 B1 C3 D4 E2 78.33
10 A3 B2 C4 D3 E1 100
11 A3 B3 C1 D2 E4 73.33
12 A3 B4 C2 D1 E3 87.97
13 A4 B1 C4 D2 E3 71.66
14 A4 B2 C3 D1 E4 73.33
15 A4 B3 C2 D4 E1 93.81
16 A4 B4 C1 D3 E2 75.47
k1 76.250 82.500 82.500 82.500 90.000 ---
k2 96.250 92.500 86.250 88.750 85.000 ---
k3 87.500 88.750 88.750 82.500 82.500 ---
k4 78.750 75.000 81.250 85.000 81.250 ---
R 20.000 17.500 7.500 6.250 8.750 ---
Table 3  Analysis of the L16(45) test results
Fig.3  XRD patterns of PANI/TiO2, PANI and TiO2
Fig.4  Nyquist plots (a) and Bode plots (b) of X70 steel painted with coatings of different formulations
Fig.5  Nyquist plots (a) and Bode plots (b) of X70 steel painted with the optimal coating after immersion in 3.5%NaCl solution at 65 ℃
Fig.6  Nyquist (a), impedance module (b) and phase angle (c) plots of X70 steel painted with the optimal coating after immersion in 3%Na2S solution for 120 h
Fig.7  SEM micrographs of the optimal coating before immersion (a), after immersion in 3.5%NaCl solution at 65 ℃ for 120 h (b) and in 3%Na2S solution at 80 ℃ for 120 h (c)
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