α-ZrP/PDMS超疏水防腐涂层的制备及其耐腐蚀性能

doi:10.16085/j.issn.1000-6613.2024-1096

摘要/Abstract

摘要：

普通的防腐涂层容易出现裂缝和间隙，抗污染性能差。本研究采用水热法合成α-磷酸锆（α-ZrP）疏水颗粒，将其嵌入聚二甲基硅氧烷（PDMS）中，构建微纳米级α-ZrP/PDMS超疏水防腐涂层。采用扫描电子显微镜、X射线衍射仪和红外光谱仪分析α-ZrP的成分和结构特征；利用电化学工作站、原子力显微镜和接触角测量仪研究α-ZrP/PDMS涂层的亲疏水性和防腐性能，考察涂层硬度和附着力的变化。结果表明：胺分子被成功引入α-ZrP层间，层间距由0.759nm扩大至1.331nm。α-ZrP颗粒具有良好的热稳定性，当温度达到400℃时，仍保持完整结构。α-ZrP纳米片在涂层中堆集成簇，通过形成空气陷阱和降低表面能，实现超疏水，水接触角为160°，表面平均粗糙度Ra=180.645nm。与裸钢相比，涂覆超疏水涂层的钢片腐蚀电流由2.31×10^-3mA/cm²下降至1.12×10^-4mA/cm²，腐蚀电位由-474.22mV提高至-447.26mV，极化电阻由8.96×10³Ω·cm²提升到7.41×10⁴Ω·cm²，防腐效率由36.20%提高至98.70%。制备的超疏水涂层的铅笔硬度为3H，附着力等级达到1级标准。超疏水防腐涂层通过在腐蚀介质和Q235钢之间形成空气膜，实现防腐和自清洁的目的。

关键词: 超疏水, 腐蚀, 聚二甲基硅氧烷, 聚合物, α-磷酸锆, 离子交换

Abstract:

Ordinary anti-corrosion coatings are prone to cracks and gaps, and their anti-pollution performance is poor. In this study, α-zirconium phosphate (α-ZrP) hydrophobic particles were synthesized using a hydrothermal method and embedded into polydimethylsiloxane (PDMS) to construct a micro nano α-ZrP/PDMS superhydrophobic anti-corrosion coating. The composition, structural characteristics and thermal stability of α-ZrP were analyzed using scanning electron microscopy (SEM), X-ray diffraction (XRD), infrared spectroscopy (FTIR) and thermogravimetric analysis (TG), respectively. The hydrophilicity and corrosion resistance of α-ZrP/PDMS coatings were studied using electrochemical workstations, atomic force microscopy (AFM) and contact angle measuring instruments, respectively. The changes in coating hardness and adhesion were investigated. The results showed that amine molecules were successfully introduced into α-ZrP layers and the layers spacing was expanded from 0.759nm to 1.331nm. The α-ZrP particles had good thermal stability and remained intact when the temperature reached 400℃. The α-ZrP nanosheets were stacked in the clusters of the coating, and air traps were formed and surface energy was reduced. The superhydrophobicity was realized and water contact angle reached 160°. The average surface roughness Ra was 180.645nm. Compared with those of bare steel, the corrosion current of steel sheets coated with superhydrophobic coatings decreased from 2.31×10^-3mA/cm² to 1.12×10^-4mA/cm², corrosion potential increased from -474.22mV to -447.26mV, polarization resistance increased from 8.96×10³Ω·cm² to 7.41×10⁴Ω·cm² and anti-corrosion efficiency improved to 98.70% from 36.20%. The pencil hardness of the coating was 3H and the adhesion grade reached grade 1 standard. The prepared super hydrophobic anticorrosive coating could achieve the purpose of anti-corrosion and self-cleaning by forming an air film between corrosive medium and Q235 steel.

Key words: superhydrophobic, corrosion, polydimethylsiloxane, polymers, α-zirconium phosphate, ion exchange

中图分类号:

TQ63

张博, 马骏, 张维隆, 贾世川, 张智飞, 丁宇, 潘有华, 王俊宇, 张兰河. α-ZrP/PDMS超疏水防腐涂层的制备及其耐腐蚀性能[J]. 化工进展, 2025, 44(9): 5130-5139.

ZHANG Bo, MA Jun, ZHANG Weilong, JIA Shichuan, ZHANG Zhifei, DING Yu, PAN Youhua, WANG Junyu, ZHANG Lanhe. Preparation of α-ZrP/PDMS superhydrophobic anti-corrosion coating and corrosion resistance performance[J]. Chemical Industry and Engineering Progress, 2025, 44(9): 5130-5139.

图/表 12

图1 α-ZrP的合成反应

图2 α-ZrP的插层反应

图3 α-ZrP、α-ZrP/PPDA和α-ZrP/DEA的SEM图

图4 α-ZrP、α-ZrP/PPDA和α-ZrP/DEA的XRD谱图和热重曲线

图5 α-ZrP、α-ZrP/PPDA和α-ZrP/DEA的红外光谱和拉曼光谱

图6 AFM 3D图及中心线轮廓

表1 α-ZrP/PDMS涂层、α-ZrP/PPDA/PDMS涂层和α-ZrP/DEA/PDMS涂层的粗糙度参数

样品	扫描面积A/μm²	最大轮廓峰高Rp/nm	轮廓的算术平均偏差Ra/nm	轮廓的均方根偏差Rq/nm	轮廓的最大高度Rz/μm	最大轮廓谷深Rv/nm
α-ZrP/PDMS涂层	100.000	600.430	172.543	210.792	1.395	753.28
α-ZrP/PPDA/PDMS涂层	100.000	689.607	180.645	224.200	1.507	817.195
α-ZrP/DEA/PDMS涂层	100.000	529.175	145.003	177.708	1.081	551.792

图7 裸钢、PDMS涂层、α-ZrP/PDMS涂层、α-ZrP/PPDA/PDMS涂层、α-ZrP/DEAPDMS涂层的Tafel曲线

表2 裸钢、PDMS涂层、α-ZrP/PDMS涂层、α-ZrP/PPDA/PDMS涂层、α-ZrP/DEA/PDMS涂层Tafel曲线腐蚀数据

样品	E_corr/mV	I_corr/mA·cm^-2	β_a/mV·dec^-1	β_c/mV·dec^-1	R_p/Ω·cm²	η/%	CR/cm³·a^-1
裸钢	-474.22	8.59×10^-3	305.256	230.598	1.17×10⁴	—	3.34
PDMS涂层	-426.38	5.48×10^-3	433.78	157.17	1.24×10⁴	36.20	2.13
α-ZrP/PDMS涂层	-458.59	1.38×10^-3	86.16	74.93	1.26×10⁴	83.93	0.54
α-ZrP/PPDA/PDMS涂层	-447.26	1.12×10^-4	165.83	165.83	7.41×10⁴	98.70	0.04
α-ZrP/DEA/PDMS涂层	-433.36	4.73×10^-4	134.87	145.93	6.43×10⁴	94.49	0.18

图8 涂料的超疏水性

图9 自清洁实验及水的弹跳性能实验(a) α-ZrP/PPDA/PDMS涂层自清洁实验；(b) PDMS涂层自清洁实验；(c) 裸钢自清洁实验；(d) 水在α-ZrP/PPDA/PDMS涂层上水的弹跳性能照片

图10 α-ZrP/PDMS涂层、α-ZrP/PPDA/PDMS涂层和α-ZrP/DEA/PDMS涂层的铅笔硬度和附着力测试结果

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