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Journal of Chinese Society for Corrosion and protection  2016, Vol. 36 Issue (1): 52-58    DOI: 10.11902/1005.4537.2015.109
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Influence of TEOS Content on Anti-corrosion Property of Mercapto Functional Organic Silane Based Sol-gel Coatings on Copper Alloy Surface
Wenjie SUI1,2,Wenjie ZHAO2(),Xing ZHANG1(),Liguang QIN1,2,Shusen PENG2,Xuedong WU2,Qunji XUE2
1. School of Materials Science and Engineering, North University of China, Taiyuan 030051, China
2. Key Laboratory of Marine Materials and Related Technologies, Zhejiang Key Laboratory of Marine Materials and Protective Technologies, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
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Abstract  

Organic-inorganic hybrid sol-gel coatings with high solid content were prepared on copper surface by means of hydrolysis-condensation reaction. 3-Mercaptopropyltrimethoxysilane (MP-TMS), tetraethylorthosilicate (TEOS) and hydrochloric acid were used as organic precursor, inorganic precursor and catalysts respectively. The chemical composition, and the average size of sol particles and the surface- and cross section-morphology of sol-gel coatings were characterized by Fourier transform infrared spectroscopy, dynamic light scattering particle size analyzer and field emission scanning electron microscopy respectively. The adhesion and corrosion performance of sol-gel coatings were investigated by pull-off adhesion tester and electrochemical workstation. The results showed that the thermo-stability of the coatings was significantly improved due to the addition of TEOS. However, the average size of sol particles increased with the increase of TEOS content. Excessive addition of TEOS can induce holes and cracks on the surface of coatings or within the coatings. The coatings owned the best corrosion resistance when the molar ratio of TEOS to MPTMS was 0.6 due to their larger crosslinking density and fewer defects.
Key words:  Cu alloy      sol-gel coating      crosslinking      corrosion resistance      thermo-stability     
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Wenjie SUI
Wenjie ZHAO
Xing ZHANG
Liguang QIN
Shusen PENG
Xuedong WU
Qunji XUE

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Wenjie SUI,Wenjie ZHAO,Xing ZHANG,Liguang QIN,Shusen PENG,Xuedong WU,Qunji XUE. Influence of TEOS Content on Anti-corrosion Property of Mercapto Functional Organic Silane Based Sol-gel Coatings on Copper Alloy Surface. Journal of Chinese Society for Corrosion and protection, 2016, 36(1): 52-58.

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https://www.jcscp.org/EN/10.11902/1005.4537.2015.109     OR     https://www.jcscp.org/EN/Y2016/V36/I1/52

Fig.1  FTIR spectra of TEOS and MPTMS
Fig.2  FTIR spectra of different coatings
Fig.3  Particle sizes of T0, T4, T6, T8 and T10 coatings
Fig.4  Surface (a, c, e, g, i) and cross section (b, d, f, h, j) morphologies of T0 (a, b), T4 (c, d), T6 (e, f), T8 (g, h) and T10 (i, j) coatings
Fig.5  Adhesion of sol-gel coatings on copper
Fig.6  Photos of copper samples before (a) and after (b) baking test
Fig.7  Potentiodynamic polarization curves of bare and covered with different coatings copper samples in 3.5%NaCl solution
Sample Icorr / Acm-2 Ecorr / mV η / %
Bare 2.250×10-6 -327 ---
T0 5.964×10-9 -412 99.73
T4 4.251×10-9 -352 99.81
T6 5.360×10-10 -445 99.97
T8 1.492×10-8 -451 99.34
T10 2.952×10-7 -498 86.88
Table 1  Electrochemical parameters obtained from polarization curves of the bare copper and sol-gel coatings covered samples
Fig.8  Impedance (a) and phase angle (b) plots of different samples
Fig.9  Nyquist plots of different samples
Fig.10  Equivalent circuits for EIS data fitting: (a)bare copper, (b) sol-gel coatings
Electrode Qfilm / Ω-1sncm-2 nfilm Rfilm / Ωcm2 Qdl / Ω-1sncm-2 ndl Rct / Ωcm2 W / Ω-1s0.5cm-2 Equivalent / circuit
Bare --- --- --- 2.238×10-5 0.8 4.382×103 1.652×10-3 R(Q(RW))
T0 5.324×10-7 0.9235 1.704×104 6.485×10-6 0.7462 3.128×105 --- R(Q(R(QR)))
T4 1.797×10-8 0.8524 2.330×104 5.916×10-7 0.7565 8.752×105 --- R(Q(R(QR)))
T6 1.290×10-9 0.8638 3.400×104 1.360×10-6 0.7454 1.205×106 --- R(Q(R(QR)))
T8 1.089×10-8 0.8 1.746×104 8.126×10-6 0.6515 2.079×105 --- R(Q(R(QR)))
T10 3.567×10-9 0.9338 2.054×104 6.690×10-6 0.7449 1.440×105 --- R(Q(R(QR)))
Table 2  Values of various elements in equivalent circuits used for EIS data fitting
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