纳米SiO<sub>2</sub>@超支化PDMS复合超疏水涂层的制备与性能调控

刘静; 雷西萍; 于婷; 陈浩男; 樊凯

doi:10.13801/j.cnki.fhclxb.20220331.002

纳米SiO₂@超支化PDMS复合超疏水涂层的制备与性能调控

doi: 10.13801/j.cnki.fhclxb.20220331.002

西安建筑科技大学　材料科学与工程学院，西安 710055

基金项目: 生态环境相关高分子材料教育部重点实验室开放基金(KF-18-01)；西安建筑科技大学基础研究基金(ZR21026)Open Foundation Provided by Key Laboratory of Eco-functional Polymer Materials of Ministry of Education (KF-18-01); Basic Research Foundation of Xi'an University of Architecture and Technology (ZR21026)

详细信息

通讯作者:
雷西萍，博士，教授，博士生导师，研究方向为超疏水材料　E-mail: leixiping123456@163.com

中图分类号: TB332
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出版历程
- 收稿日期: 2022-01-13
- 修回日期: 2022-03-12
- 录用日期: 2022-03-19
- 网络出版日期: 2022-04-01
- 刊出日期: 2023-02-15

Construction and property regulation of nano-SiO₂@hyperbranched PDMS composite superhydrophobic coating

School of Materials Science and Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China

摘要

摘要: 超疏水涂层在实际应用中受化学腐蚀、刮擦磨损等外界环境的影响，易造成涂层老化、开裂甚至脱落，造成涂层失效。因此，针对这一问题，设计出具备耐候性的自修复超疏水表面：以超支化聚二甲基硅氧烷为柔性基底和低表面能物质，引入纳米二氧化硅构筑表面粗糙结构，制备超疏水涂层。当SiO₂粒径为50 nm、固含量为30wt%时，得到了接触角为154.87°的超疏水涂层。经过5次胶带剥离试验，涂层表现出良好的机械稳定性。经历10次温差循环试验和24 h紫外光照射后，涂层表面接触角仍大于150°，表明涂层具有良好的耐候性。涂层经过80℃、2 h的热处理可修复划痕，表明该涂层具有一定的自修复功能。同时，Tafel及Nyquist测试结果表明，对基底进行超疏水处理可显著提高防腐性能，并且该涂层具有明显的自清洁效果。综上所述，本文所制备的纳米SiO₂@超支化聚二甲基硅氧烷(PDMS)复合超疏水涂层具有自修复功能，为自修复超疏水涂层的开发提供了新的研究策略。
- 超疏水涂层 /
- 自修复 /
- 二氧化硅 /
- 耐候性 /
- 耐久性
Abstract: In practical application, affected by chemical corrosion, scratch and wear and other external environment, superhydrophobic coating is easy to aging, cracking and even falling off, resulting in coating failure. Therefore, to solve this problem, a self-healing superhydrophobic surface with weather resistance was designed: Hyperbranched polydimethylsiloxane (PDMS) was used as a flexible substrate and low surface energy material, and nano-silica was introduced to construct the surface rough structure to prepare the superhydrophobic coating. When SiO₂ particle size is 50 nm and solid content is 30wt%, the superhydrophobic coating with contact angle of 154.87° is obtained. The coating shows good mechanical stability after 5 times of tape peeling test. After 10 temperature difference cycling tests and 24 h UV irradiation, the surface contact angle is still greater than 150°, indicating that the coating has good weather resistance. The scratches can be partially healed by heat treatment at 80℃ for 2 h, indicating that the coating has certain self-healing function. At the same time, Tafel and Nyquist test results indicates that superhydrophobic treatment can significantly improve the corrosion resistance of the substrate, and the coating has obvious self-cleaning effect as well. In conclusion, the nano-SiO₂@hyperbranched PDMS composite superhydrophobic coating prepared in this work has self-healing function, which provides a new research strategy for the development of self-healing superhydrophobic coating.
- superhydrophobic coating /
- self-healing /
- SiO₂ /
- weather resistance /
- durability

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图 1 超疏水涂层的制备过程示意图

TMC—Trimesoyl chloride; A-PDMS—Diaminopropyl terminated polydimethylsiloxane; HB-PDMS—Hyperbranched polydimethylsiloxane; SiO₂@HB-PDMS—SiO₂@hyperbranched polydimethylsiloxane composite

Figure 1. Schematic diagram of preparation of superhydrophobic coating

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图 2 超支化聚二甲基硅氧烷(HB-PDMS)的反应机制和复合涂层化学结构表征：(a)HB-PDMS的化学结构；(b)A-PDMS、均苯三甲酰氯(TMC)和HB-PDMS的¹H NMR图谱；HB-PDMS的¹³C NMR图谱(c)和凝胶渗透色谱(GPC)分子量分布曲线(d)；(e)A-PDMS、HB-PDMS、SiO₂和SiO₂@HB-PDMS涂层的FTIR图谱

Figure 2. Reaction mechanism of hyperbranched-polydimethyl siloxane (HB-PDMS) and chemical structure characterization of composite coatings: (a) Chemical structure of HB-PDMS; (b) ¹H NMR spectra of A-PDMS, trimesoyl chloride (TMC) and HB-PDMS; ¹³C NMR spectra (c) and molecular weight distribution curves (d) of gel permeation chromatography (GPC) of HB-PDMS; (e) FTIR spectra of A-PDMS, HB-PDMS, SiO₂ and SiO₂@HB-PDMS coatings

δ—Chemical shift; THF—Tetrahydrofuran; dw/dlgM—Quantity distribution of polymers with different molecular weights

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图 3 不同SiO₂粒径及固含量对SiO₂@HB-PDMS复合涂层润湿性的影响

Figure 3. Effect of different SiO₂ particle size and solid content on the wettability of SiO₂@HB-PDMS composite coatings

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图 4 SiO₂@HB-PDMS超疏水涂层的胶带剥离测试结果

Figure 4. Tape peeling test results of SiO₂@HB-PDMS superhydrophobic coatings

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图 5 添加不同固含量SiO₂纳米颗粒的SiO₂@HB-PDMS复合涂层的微观形貌((a)~(d))与元素组成(e)

Figure 5. Microstructure ((a)-(d)) and elemental composition (e) of SiO₂@HB-PDMS composite coatings with different solid content of SiO₂ nanoparticles

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图 6 超支化PDMS涂层((a), (b))和SiO₂@HB-PDMS超疏水涂层((c)~(f))的自修复光学显微镜照片；差示扫描量热曲线(g)和修复前后Tafel测试结果((h), (i))

Figure 6. Self-healing optical microscope images of hyperbranched-PDMS coatings ((a), (b)) and SiO₂@HB-PDMS superhydrophobic coatings ((c)-(f)), DSC curves (g) and Tafel results ((h), (i)) before and after self-healing of hyperbranched-PDMS coatings and SiO₂@HB-PDMS superhydrophobic coatings

T_g—Glass transition temperature; i—Corrosion current density

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图 7 HB-PDMS涂层和SiO₂@HB-PDMS涂层的温差试验 (a) 和耐紫外老化试验结果 (b)

Figure 7. Transmission spectra (a) and UV aging resistance test (b) of the HB-PDMS and SiO₂@HB-PDM coatings

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图 8 涂覆SiO₂@HB-PDMS涂层前后试样的电化学测试结果：(a) Tafel极化曲线；(b) Nyquist图

Figure 8. Electrochemical test results of samples before and after SiO₂@HB-PDMS coating: (a) Tafel polarization curve; (b) Nyquist diagram

R_s—Solution resistance between the reference electrode and specimens; R_ct—Charge transfer resistance; R_coat—Resistance of the superhydrophobic coating; C_dl, C_coat—Double layer capacitance on metal surface and capacitance on coating itself, respectively; W—Warburg resistance

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图 9 未处理玻璃 (a) 和SiO₂@HB-PDMS超疏水涂层玻璃 (b) 的自清洁测试

Figure 9. Self-cleaning properties of uncoated glass (a) and SiO₂@HB-PDMS superhydrophobic coated glass (b)

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表 1 不同SiO₂粒径及固含量的SiO₂@HB-PDMS复合涂层的划格试验测试结果

Table 1. Classification of cross-cut test results of SiO₂@HB-PDMS composite coatings with different SiO₂ particle size and solid content

SiO₂ particle size/nm	Cross-cut test results
SiO₂ particle size/nm	20wt%SiO₂	30wt%SiO₂	40wt%SiO₂	50wt%SiO₂	60wt%SiO₂
30	0	1	2	4	5
50	0	0	3	4	5
500	0	3	2	4	5

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表 2 从极化曲线获得的HB-PDMS和SiO₂@HB-PDMS涂层自修复测试前后的腐蚀参数

Table 2. Corrosion parameters obtained from potentiodynamic polarization curves with the self-healing tests on HB-PDMS and SiO₂@HB-PDMS coatings

Samples		E_corr/mV	i/(μA·cm⁻²)
HB-PDMS	Original	188.2	0.330
	Scratched	171.6	0.486
	Healed	182.3	0.472
SiO₂@HB-PDMS	Original	197.3	0.560
	Scratched	−1091.3	0.886
	Healed	−663.1	0.802
Note: E_corr—Corrosion potential.

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