POSS改性氧化石墨烯对涂层防腐和疏水性能的影响

doi:10.11949/0438-1157.20240196

摘要/Abstract

摘要：

通过有机硅化合物γ-氨丙基三乙氧基硅烷（APTES）自水解缩合制得有机-无机杂化材料笼型倍半硅氧烷（POSS），将其接枝到氧化石墨烯（graphene oxide，GO）上以克服GO的聚集，利用Boehm滴定法测定接枝率为98.3%，进一步负载锌离子制得复合纳米粒子POSS/GO/Zn。通过FT-IR、XRD、Raman、NMR和SEM对POSS/GO/Zn结构及微观形貌进行了表征，并将其应用在水性环氧树脂（WEP）涂层材料中，电化学阻抗谱（EIS）和水接触角测试结果表明，所制得的纳米粒子的复合涂层具有优异的防腐和疏水性能，在3.5%氯化钠溶液中浸泡40 d后POSS/GO/Zn/WEP的阻抗值为8.33×10⁵ Ω·cm²，大于空白环氧涂层浸泡第一天的初始值1.46×10⁵ Ω·cm²，水接触角由48.42°增大至98.11°，涂层由亲水转为疏水特性，表明该材料在涂层材料中具有良好的应用潜能。

关键词: 腐蚀, 表面, 纳米材料, 氧化石墨烯

Abstract:

The cage sesquisiloxane (POSS) of organic-inorganic hybrid material was prepared by self-hydrolytic condensation of organosilicon compound γ-aminopropyl triethoxysilane (APTES),and then it was grafted onto graphene oxide (GO) to overcome aggregation of GO. The grafting rate was determined to be 98.3% by Boehm titration, and further loaded with zinc ions to prepare composite nanoparticles POSS/GO/Zn. The structure and microstructure of POSS/GO/Zn were characterized with FT-IR, XRD, Raman, NMR, and SEM, and applied to waterborne epoxy resin (WEP) coating materials. The electrochemical impedance spectroscopy (ESI) and water contact angle results showed that the composite coating of the obtained nanoparticles presented the excellent anti-corrosion and hydrophobic properties. The impedance value of POSS/GO/Zn/WEP after being soaked in 3.5% sodium chloride solution for 40 days was 8.33×10⁵ Ω·cm², which was greater than the initial value of 1.46×10⁵ Ω·cm² on the first day of immersion of the blank epoxy coating. The water contact angle increased from 48.42° to 98.11°, and the property of coating changed from hydrophilic to hydrophobic,indicating that the POSS/GO/Zn has good potential for application in coatings.

Key words: corrosion, surface, nanomaterials, graphene oxide

中图分类号:

TQ 630.4

赵璐璐, 唐二军, 邢旭腾, 刘少杰, 褚晓萌, 呼娜, 张泽. POSS改性氧化石墨烯对涂层防腐和疏水性能的影响[J]. 化工学报, 2024, 75(5): 1977-1986.

Lulu ZHAO, Erjun TANG, Xuteng XING, Shaojie LIU, Xiaomeng CHU, Na HU, Ze ZHANG. Effects of POSS modified graphene oxide in anti-corrosion and hydrophobic properties of coatings[J]. CIESC Journal, 2024, 75(5): 1977-1986.

图/表 11

表1 空白及复合环氧涂料的配比

Table 1 The ratio of blank and composite epoxy coatings

组分	改性环氧复合涂料	环氧涂料（空白）
水性环氧乳液	19.66	19.66
固化剂	15.66	15.66
润湿剂	0.34	0.34
增稠剂	0.17	0.17
消泡剂	0.17	0.17
POSS/GO/Zn	0.015	0

图1 POSS(a)，POSS/GO(b)和POSS/GO/Zn(c)功能材料的制备反应过程

Fig.1 Preparation of POSS (a), POSS/GO (b) and POSS/GO/Zn (c) functional materials

图2 POSS/GO/Zn功能材料及水性复合涂层的制备机理

Fig.2 Preparation mechanism of POSS/GO/Zn and waterborne composite epoxy coating

图3 POSS的核磁氢谱(a)，核磁碳谱(b)和XRD谱图(c)

Fig.3 1H NMR spectra (a), 13C NMR spectra (b) and XRD pattern (c) of POSS

图4 GO、POSS/GO和POSS/GO/Zn的红外光谱图(a)和XRD谱图(b)

Fig.4 FT-IR spectra (a) and XRD patterns (b) of nanomaterials GO,POSS/GO and POSS/GO/Zn

图5 GO、POSS/GO的拉曼光谱图

Fig.5 Raman plots of nanomaterials GO and POSS/GO

图6 GO(a)、POSS/GO(b)和POSS/GO/Zn(c)的SEM图及POSS/GO/Zn的EDS图(d)

Fig.6 SEM images of GO (a), POSS/GO (b) and POSS/GO/Zn (c) and EDS polts of POSS/GO/Zn (d)

图7 在3.5%氯化钠溶液中浸泡不同时间的Nyquist和Bode图：(a)~(c)WEP； (d)~(f) GO/WEP； (g)~(i)POSS/GO/WEP； (j)~(l)POSS/GO/Zn/WEP

Fig.7 The Nyquist and Bode plots of WEP [(a)—(c)], GO/WEP [(d)—(f)], POSS/GO/WEP [(g)—(i)], and POSS/GO/Zn/WEP [(j)—(l)] after immersion for different durations in 3.5%(mass) NaCl solution

图8 在3.5%氯化钠溶液中浸泡10 d后的涂层极化曲线

Fig.8 The curve of polarization of composite coatings soaking in 3.5% NaCl solution for 10 d

图9 不同涂层的耐盐雾实验结果

Fig.9 The salt spray test results of different coatings

图10 不同填料对涂层的水接触角的影响

Fig.10 Effect of different fillers on the water contact angle of the coating

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