热场辅助机械力化学法制备界面化学键合防腐涂层

doi:10.12068/j.issn.1005-3026.2025.20240214

摘要/Abstract

摘要：

涂料体系中填料/树脂的界面相容性是提高涂层防护性能的关键.有机防腐涂层中常用的云母填料经过处理后，采用常温、不同温度热场辅助条件下的机械力化学法制备云母-环氧树脂改性填料，通过傅里叶变换红外光谱（FTIR）、热重分析（TGA）等测试评价了填料/涂层界面化学键合的可行性.结果表明，热场辅助机械力化学法可实现常规情况下树脂与云母不易进行的化学反应.通过耐蚀测试证明了添加改性云母的环氧涂层具有更优异的耐蚀性能，同时探讨了改性云母填料对涂层的作用机理，为热场辅助机械力化学法调控环氧涂层防腐性能研究提供了理论依据.

关键词: 防腐涂层, 界面化学键合, 环氧树脂, 云母, 热场辅助机械力化学

Abstract:

The interfacial compatibility of fillers/resins in coating systems is the key to improving the protection performance of coatings. Mica fillers commonly used in organic anticorrosive coatings were first processed， and mica-epoxy resin modified fillers were prepared by mechanochemistry methods under the auxiliary conditions of normal temperatures and different temperature thermal fields. The feasibility of interfacial chemical bonding between fillers and coatings was evaluated by Fourier transform infrared spectroscopy （FTIR） and thermogravimetric analysis（TGA）. The results show that thermal field-assisted mechanochemistry can realize the chemical reaction between resin and mica， which is difficult to proceed under normal conditions. The corrosion resistance test proves that the epoxy coating with modified mica has better corrosion resistance， and the action mechanism of modified mica filler on the coating is discussed， which provides a theoretical basis for the study of thermal field-assisted mechanochemical control of the corrosion resistance of epoxy coating.

Key words: anticorrosive coating, interfacial chemical bonding, epoxy resin, mica, thermal field-assisted mechanochemistry

中图分类号:

TG 174.4

孟凡帝, 万心语, 蔡亚慧, 刘莉. 热场辅助机械力化学法制备界面化学键合防腐涂层[J]. 东北大学学报（自然科学版）, 2025, 46(8): 113-123.

Fan-di MENG, Xin-yu WAN, Ya-hui CAI, Li LIU. Interface Chemical Bonded Anticorrosion Coatings of Prepared by Thermal Field-Assisted Mechanochemistry[J]. Journal of Northeastern University(Natural Science), 2025, 46(8): 113-123.

图/表 15

表1 Q235钢的化学成分（质量分数） ((mass fraction) %)

Table 1 Chemical composition of Q235 steel

C	Si	Mn	P	S	Fe
0.17	0.35	1.40	0.012	0.015	余量

图1 可加热球磨机的结构

Fig.1 Structure of heatable ball mill

图2 天然云母与常温下不同转速机械力化学处理云母后的粉末表征结果（a）—填料粉末的红外光谱；（b）—填料粉末的热重结果；（c）—填料粉末的接触角结果.

Fig.2 Powder characterization results of untreated mica and mechanochemically treated mica at different rotational speeds at room temperature

图3 天然云母与不同温度加热处理后的云母粉末表征结果（a）—填料粉末的红外光谱；（b）—填料粉末的热重结果；（c）—填料粉末的接触角结果.

Fig.3 Characterization results of untreated mica and heated mica at different temperatures

图4 热场辅助机械力化学法处理后的云母粉末表征结果（a）—填料粉末的红外光谱；（b）—填料粉末的热重结果；（c）—填料粉末的接触角结果；（d）—热场辅助机械力法处理填料与其他状态的填料7 d沉降测试结果对比.

Fig.4 Characterization results of mica treated by thermal field-assisted mechanochemistry

图5 云母填料的TEM 图像（a）—天然云母填料；（b）—160 ℃，500 r/min热场辅助机械力化学法处理后的云母填料.

Fig.5 TEM images of mica filler

图6 天然云母粉末XPS 结果（a）—全谱扫描；（b）—C元素高分辨扫描拟合谱；（c）—O元素高分辨扫描拟合谱；（d）—Si元素高分辨扫描拟合谱.

Fig.6 XPS results of untreated mica power

图7 160 ℃，600 r/min热场辅助机械力化学法处理后云母粉末的XPS谱（a）—全谱扫描；（b）—C元素高分辨扫描拟合谱；（c）—O元素高分辨扫描拟合谱；（d）—Si元素高分辨扫描拟合谱.

Fig.7 XPS spectra of mica power treated by thermal field-assisted mechanochemistry at 160 °C and 600 r/min

图8 不同处理条件下的云母粒径分布曲线（a）—常温条件下不同转速球磨；（b）—不同温度加热后的球磨.

Fig.8 Mica particle size distribution curves under different processing conditions

图9 云母表面接枝环氧树脂化学反应示意图（a）—改性云母/环氧树脂涂层；（b）—未改性云母/环氧树脂涂层.

Fig.9 Schematic diagram of chemical reaction of grafting epoxy on surface of mica

图10 云母/环氧树脂自由膜涂层在3.5% NaCl溶液中的吸水率曲线

Fig.10 Water absorption curves of mica/epoxy film in 3.5% NaCl solution

图11 涂层浸泡不同时间的电化学阻抗谱波特图（a）—改性云母/环氧树脂涂层；（b）—天然云母/环氧树脂涂层.

Fig.11 Bode plots of electrochemical impedance spectra of coatings with different immersion times

图12 改性前后云母/环氧树脂涂层在质量分数为3.5%的NaCl溶液浸泡3 840 h后的表面形貌（a）—天然云母/环氧树脂涂层；（b）—改性云母/环氧树脂涂层.

Fig.12 Surface morphology of mica/epoxy coating before and after modification after immersion in 3.5% NaCl solution for 3 840 h

图13 云母/环氧树脂涂层服役后的截面SEM 图像（a）—改性云母/环氧树脂涂层；（b）—天然云母/环氧树脂涂层.

Fig.13 SEM images of cross-section of mica/epoxy coating in service

图14 云母/环氧树脂涂层对金属基体腐蚀保护机理（a）—天然云母/环氧树脂涂层；（b）—未改性云母/环氧树脂涂层.

Fig.14 Corrosion protection principle of mica/epoxy coating on metal substrates

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