环氧树脂/硅基-纳米SiO2涂层的制备及防腐蚀性能

doi:10.7503/cjcu20170821

摘要/Abstract

摘要：

采用硅氢加成反应制备了2-(3,4-环氧环己基)乙基三乙氧基硅烷(ETEO), 用ETEO对纳米SiO₂进行表面接枝得到新型硅基纳米SiO₂(ETEO-SiO₂), 并制备环氧树脂/ETEO-SiO₂复合涂层. 利用傅里叶变换红外光谱(FTIR)、氢核磁共振谱(¹H NMR)与X射线光电子能谱分析(XPS)对ETEO和ETEO-SiO₂进行了表征. 场发射扫描电子显微镜(FESEM)观察到ETEO-SiO₂涂层横截面粗糙, ETEO-SiO₂具有良好分散性. 接触角分析表明ETEO-SiO₂涂层疏水性提高. 利用电化学阻抗实验与盐雾实验研究了复合涂层的防腐蚀性能, 结果表明, 添加ETEO-SiO₂纳米粒子后涂层的防腐蚀性能远优于纯环氧树脂和纳米SiO₂复合环氧树脂涂层, 当ETEO-SiO₂纳米粒子添加量达到4%(质量分数)时, 防腐蚀性能最佳. 纳米SiO₂表面接枝ETEO后, ETEO-SiO₂纳米粒子与环氧树脂基体之间的相容性增加, 分散稳定性提高, 涂层更加致密, 减少了腐蚀介质所需的扩散通道并抑制腐蚀反应过程的进行, 提高了复合涂层的防腐蚀性能.

关键词: 复合涂层, 硅基纳米二氧化硅, 环氧树脂, 表面接枝, 防腐蚀性能

Abstract:

2-(3,4-Epoxycyclohexyl) ethyltriethoxysilane(ETEO) was synthesized by a highly effective hydrosilylation reaction using 1,2-epoxy-4-vinylcyclohexane and triethoxysilane as substrates and Karstedt catalyst as the catalyst. Different methods were employed to characterize the coatings. The surface of nano-silica was treated with ETEO in order to obtain a new silane grafted on nano-silica(ETEO-SiO₂). The structure of ETEO was characterized by means of ¹H nuclear magnetic resonance spectrometer and Fourier transform infrared spectroscopy. The X-ray photoelectron spectroscopy showed that ETEO was successfully grafted on nano-silica. In addition, the morphology of the coating cross section and dispersion of ETEO-SiO₂ were investigated by field emission scanning electron microscopy. The wettability of the coating surface was analyzed by the contact angle measurement. The electrochemical impedance spectroscopy(EIS) and salt spray test of the composite coatings revealed that the corrosion resistance of coatings with ETEO-SiO₂ nanoparticles was signiﬁcantly improved as compared with that of the epoxy(EP) and SiO₂/EP coatings. Corrosion resistance achieved the highest value when ETEO-SiO₂ content reached 4%(mass fraction). It can be indicated that the SiO₂ nano-particles grafted by ETEO enhanced its compatibility effectively in the organic matrix so that ETEO-SiO₂ could distribute in the epoxy resin evenly. What’s more, the ETEO-SiO₂ increased the shielding effect of the coating and filled the coating defects, which can reduce the corrosive diffusion channels and inhibit the progress of the corrosion reaction.

Key words: Composite coating, Silane grafted nano-silica, Epoxy resin, Surface treatment, Anticorrosion property

中图分类号:

O633.13

TrendMD:

王英楠, 戴雪岩, 徐天璐, 曲立杰, 张春玲. 环氧树脂/硅基-纳米SiO₂涂层的制备及防腐蚀性能. 高等学校化学学报, 2018, 39(7): 1564.

WANG Yingnan, DAI Xueyan, XU Tianlu, QU Lijie, ZHANG Chunling. Preparation and Anticorrosion Properties of Silane Grafted Nano-silica/Epoxy Composite Coating^†. Chem. J. Chinese Universities, 2018, 39(7): 1564.

图/表 13

Scheme 1 Schematic reaction of VCHO and triethoxysilane

Scheme 2 Schematic illustration of the surface treatment of nano SiO2

Fig.1 FTIR(A) and 1H NMR(B) spectra of triethoxysilane(a), VCHO(b) and ETEO(c)

Fig.2 XPS full spectrum(A) and C1s(B), O1s(C), Si2p(D) spectra of ETEO-SiO2

Fig.3 SEM images of coating cross section of EP(A), SiO2/EP(B) and 1%—5%ETEO-SiO2/EP coatings(C—G)

Fig.4 Typical Si mapping micrographs of the 4%ETEO-SiO2/EP coating^ (A) Digital image; (B) Si mapping.

Fig.5 Water contact angle(CA) values of EP(A), SiO2/EP(B) and 1%—5%ETEO-SiO2/EP(C—G) coatings^(A) CA=62.6°; (B) CA=42.7°; (C) CA=65.6°; (D) CA=67.2°; (E) CA=70.4°; (F) CA=83.7°; (G) CA=76.1°.

Fig.6 Bode diagrams of the EP, SiO2/EP and 1%—5%ETEO-SiO2/EP samples immersed in 3.5%NaCl solution for 10 h(A, B), 100 h(C, D), 500 h(E, F) and 1500 h(G, H)^ (A, C, E, G) Frequency vs. |Z|; (B, D, F, H) frequency vs. phase angle.

Fig.7 Nyquist diagrams of the EP, SiO2/EP and 1%—5%ETEO-SiO2/EP samples immersed in 3.5% NaCl solution for 10 h(A), 100 h(B), 500 h(C) and 1500 h(D—F)

Fig.8 Equivalent circuit models used to perform EIS data

Table 1 Electrochemical parameters from the equivalent electrical circuits

Time/h	EP		SiO₂/EP		4%ETEO-SiO₂/EP
Time/h	R_c/(Ω∙cm²)	CPE/(F∙cm^-2)	R_c/(Ω∙cm²)	CPE/(F∙cm^-2)	R_c/(Ω∙cm²)	CPE/(F∙cm^-2)
10	6.395×10⁹	4.873×10^-10	7.686×10⁹	2.594×10^-10	1.863×10¹¹	3.534×10^-12
100	1.806×10⁹	1.058×10^-10	2.805×10⁹	8.362×10^-9	9.163×10¹⁰	8.658×10^-11
500	6.385×10⁸	3.246×10^-9	1.472×10⁹	6.424×10^-9	6.694×10¹⁰	3.547×10^-11
1500	6.806×10⁶	9.832×10^-7	9.235×10⁶	1.207×10^-7	2.845×10¹⁰	3.644×10^-10

Fig.9 Photographs of EP(A), SiO2/EP(B) and 1%—5% ETEO-SiO2/EP coatings(C—G) after salt spray test for 400 h

Fig.10 Corrosive protection mechanism graph of the SiO2/EP(A) and 4%ETEO-SiO2/EP(B) coatings

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环氧树脂/硅基-纳米SiO₂涂层的制备及防腐蚀性能

Preparation and Anticorrosion Properties of Silane Grafted Nano-silica/Epoxy Composite Coating^†

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