Preparation and corrosion resistance of SiO2 or TiO2 nano particles/fluorinated polyacrylate polymer composite coatings
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摘要: 通过在含氟聚丙烯酸酯(PFHI)溶液中添加固体纳米粒子,经涂覆热固化后得到了厚度约为1 μm的SiO2或TiO2纳米粒子/PFHI复合涂层,考察了SiO2或TiO2两种纳米粒子质量分数对复合涂层表面性质和防腐蚀性能的影响。利用Tafel极化曲线和电化学交流阻抗(EIS)测试研究了复合涂层在3.5wt% NaCl溶液中的电化学防腐蚀性能,并运用XPS、衰减全反射傅里叶变换红外光谱(ATR-FTIR)、TG-DTA、SEM、光学接触角(OCA)手段对复合涂层进行表征。结果表明,添加SiO2或TiO2纳米粒子均可大幅提高PFHI涂层的电化学防腐蚀性能,SiO2与PFHI质量比为0.3的SiO2/PFHI复合涂层电荷转移阻抗值Rct与PFHI涂层相比上升了2个数量级。SiO2或TiO2纳米粒子增大了涂层表面粗糙度,与PFHI紧密结合形成致密的复合涂层,提高了涂层的疏水性和致密性,从而改善了涂层的抗腐蚀性能。Abstract: SiO2 or TiO2 nanoparticles/fluorinated polyacrylate polymer (PFHI) composite coatings with thickness of 1 μm were prepared by incorporating nanoparticles into PFHI solution followed by dip-coating and thermal curing. The effects of the amount of SiO2 or TiO2 nanoparticles on the surface properties and corrosion resistance of the composite coatings were investigated. The corrosion electrochemical property of the SiO2 or TiO2/PFHI composite coatings in 3.5wt% NaCl solution was investigated by Tafel curves and electrochemical impedance spectroscopy (EIS). XPS, attenuated total reflection Fourier transform infrared (ATR-FTIR), TG-DTA, SEM, optical contact angle (OCA) were used to characterize the composite coatings. The results show that the addition of SiO2 or TiO2 nanoparticles could greatly improve the corrosion resistance of the PFHI coatings. The SiO2/PFHI composite coating with SiO2 to PFHI of 0.3 in mass ratio exhibits the best electrochemical corrosion resistance performance and the penetration resistance Rct is increased by two order of magnitude compared with the neat PFHI coating. The SiO2 or TiO2 nanoparticles combine with the PFHI tightly and increase the coating surface roughness to form the compact composite coatings, improving the hydrophobicity and compactness and the corrosion resistance of SiO2 or TiO2/PFHI composite coatings.
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表 1 SiO2或TiO2/含氟聚丙烯酸酯(PFHI)涂层配方
Table 1. Recipe of SiO2 or TiO2/fluorinated polyacrylate polymer (PFHI) coatings
Sample 5wt% PFHI
solution/gNano particle/g Nano particle:
PFHI (Mass ratio)0.1SiO2/PFHI 10 0.05 0.1 0.2SiO2/PFHI 0.10 0.2 0.3SiO2/PFHI 0.15 0.3 0.4SiO2/PFHI 0.20 0.4 0.1TiO2/PFHI 10 0.05 0.1 0.2TiO2/PFHI 0.10 0.2 0.3TiO2/PFHI 0.15 0.3 0.4TiO2/PFHI 0.20 0.4 表 2 TiO2/PFHI复合材料涂层的Tafel极化曲线拟合数据
Table 2. Fitting data of Tafel polarization curves for TiO2/PFHI composite coatings
Sample Icorr/10−9 (A·cm−2) Ecorr/
mVCorrosion rate/10−5
(mm·a−1)βc βa Pe/
%Blank 1 501 −312 1 741 7.35 6.620 — PFHI 7.570 −197 8.780 8.12 37.93 99.5 0.1TiO2/PFHI 3.110 −168 3.610 8.03 3.620 99.8 0.2TiO2/PFHI 16.08 −247 18.66 8.20 2.910 99.0 0.3TiO2/PFHI 12.59 −126 14.61 8.78 28.21 99.2 0.4TiO2/PFHI 91.10 −254 105.7 7.76 3.200 94.0 Notes: Icorr—Corrosion current density; Ecorr—Corrosion electric potential; βc—Cathode Tafel slope; βa—Anode Tafel slope; Pe—Protection efficiency in the electrochemical corrosion experiments. 表 3 SiO2/PFHI和TiO2/PFHI复合涂层的EIS曲线拟合数据
Table 3. Fitting data of EIS curves of SiO2/PFHI and TiO2/PFHI composite coatings
Sample Rs/(Ω·cm2) Rct/106 (Ω·cm2) Y0/10−7 n Blank 6.36 0.07 321 0.874 PFHI 74.68 3.91 5.93 0.869 0.1SiO2/PFHI 125.4 25.2 1.06 0.844 0.2SiO2/PFHI 146.3 56.2 0.262 0.856 0.3SiO2/PFHI 126.2 328 0.016 0.962 0.4SiO2/PFHI 135.8 263 12.8 0.875 0.1TiO2/PFHI 159.2 42.5 59.0 0.781 0.2TiO2/PFHI 154.0 3.23 1.32 0.747 0.3TiO2/PFHI 147.7 3.53 1.72 0.706 0.4TiO2/PFHI 118.1 2.37 1.04 0.774 Notes: Rs—Solution impedance; Rct—Charge transfer resistance; Y0—Constant of constant phase element(CPE); n—Surface roughness of the surface of phase shifting working electrode. 表 4 涂覆涂层碳钢在6wt% FeCl3溶液中的质量损失
Table 4. Mass loss of coated carbon steel in 6wt% FeCl3 solution
Sample mloss/mg RM /% Pc/% Blank 149.9 1.75 0 PFHI 126.0 1.47 15.9 0.1SiO2/PFHI 109.6 1.28 26.9 0.2SiO2/PFHI 106.6 1.25 28.9 0.3SiO2/PFHI 77.3 0.90 48.4 0.4SiO2/PFHI 108.7 1.28 27.5 0.1TiO2/PFHI 94.8 1.10 36.8 0.2TiO2/PFHI 127.0 1.47 15.3 0.3TiO2/PFHI 125.8 1.47 16.1 0.4TiO2/PFHI 137.6 1.60 8.2 Notes: mloss—Mass loss of the sample after the chemical corrosion experiments; RM—Percentage of mass loss; Pc—Protection efficiency in the chemical corrosion experiments. 表 5 PFHI、0.1TiO2/PFHI和0.3SiO2/PFHI涂层表面元素含量
Table 5. Surface element contents of PFHI, 0.1TiO2/PFHI and 0.3SiO2/PFHI coatings
Coating F/at% C/at% O/at% F/C Ti or Si/at% PFHI 47.37 43.42 7.96 1.09 — 0.1TiO2/PFHI 46.64 42.90 8.64 1.09 0.76 0.3SiO2/PFHI 38.66 39.86 15.24 0.97 4.66 -
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