阻垢涂层中纳米填料的研究进展

doi:10.16085/j.issn.1000-6613.2024-1605

摘要/Abstract

摘要：

纳米填料具有尺寸小、比表面积高等优点，将纳米填料引入阻垢涂层可进一步提高阻垢涂层的阻垢效果，因此含纳米填料的复合阻垢涂层受到了广泛的关注。本文从纳米填料加入复合涂层后的阻垢机理入手，总结分析纳米填料在阻垢涂层中的作用机理主要有：①低表面能降低成垢物质的成核速率、生长速度及成垢物质在涂层表面的附着力；②表面微纳结构诱发垢层形成不稳定的晶体结构或抑制晶体形核。此外，介绍了纳米二氧化硅、碳纳米材料（碳纳米管、碳纳米纤维、石墨烯及其衍生物等）、纳米金属氧化物（TiO₂、CeO₂、ZnO）等常用纳米填料的性质及引入涂层后存在的优缺点，总结了纳米填料及阻垢涂层的制备过程及方法，并对纳米填料在阻垢涂层方面的研究方向进行了展望，以期为纳米填料在防垢复合涂层领域的应用提供一定的参考。

关键词: 纳米填料, 涂层, 阻垢

Abstract:

Nano-fillers have the advantages of small size and high specific surface area. The introduction of nano-fillers into scale inhibition coatings can further improve the scale inhibition effect of scale inhibition coatings. Therefore, the research and application of composite scale inhibition coatings containing nano-fillers have received extensive attention. In this paper, the scale inhibition mechanism of nano-fillers after adding composite coatings was studied, and the mechanism of nano-fillers in scale inhibition coatings was summarized and analyzed: ① Low surface energy could reduce the nucleation rate, growth rate and adhesion of fouling substances on the coating surface; ② The surface micro-nano structure induced the scale layer to form an unstable crystal structure or inhibited crystal nucleation. In addition, the properties of nano-silica, carbon nanomaterials (carbon nanotubes, carbon nanofibers, graphene and its derivatives, etc.), nano-metal oxides (TiO₂, CeO₂, ZnO) and other commonly used nano-fillers and the advantages and disadvantages after the introduction of coatings were introduced. The preparation process and methods of nano-fillers and scale inhibition coatings were summarized, and the research direction of nano-fillers in scale inhibition coatings was prospected in order to provide some reference for the application of nano-fillers in the field of anti-scaling composite coatings.

Key words: nano-fillers, coating, scale inhibition

中图分类号:

TG174.4

赵敏, 徐静, 郭兴建, 陈昇, 李鹏洁, 何萌. 阻垢涂层中纳米填料的研究进展[J]. 化工进展, 2025, 44(4): 2183-2195.

ZHAO Min, XU Jing, GUO Xingjian, CHEN Sheng, LI Pengjie, HE Meng. Research progress of nano-fillers in scale inhibition coatings[J]. Chemical Industry and Engineering Progress, 2025, 44(4): 2183-2195.

图/表 12

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纳米填料	性质	涂层特点	参考文献
碳纳米管（CNTs）	强度高、韧性好、稳定性好、疏水性	分散性差、疏水性好	[48-50]
碳纳米纤维（CNFs）	耐高温	机械强度好、相容性差、比表面积大、分散性差	[6,15,51]
石墨烯及其衍生物	比表面积大、强度高	化学稳定性好、分散性差、界面相容性差等	[26,52-54]

纳米填料	性质	涂层特点	参考文献
碳纳米管（CNTs）	强度高、韧性好、稳定性好、疏水性	分散性差、疏水性好	[48-50]
碳纳米纤维（CNFs）	耐高温	机械强度好、相容性差、比表面积大、分散性差	[6,15,51]
石墨烯及其衍生物	比表面积大、强度高	化学稳定性好、分散性差、界面相容性差等	[26,52-54]

序号	纳米填料	制备方法	优点	缺点	复合涂层	涂层性能	其他功能
1	纳米SiO₂^[6,47]	共混法	操作简单、适合大规模生产、适用多种基体材料，可灵活调控填料的种类、含量	分散性差、易团聚、填料与基体间界面相互作用弱	超疏水聚偏氟乙烯/氟化乙丙烯/二氧化硅（PFS）复合涂层	结垢率仅为疏水PFS复合涂层的44%	—
2					PPS/PTFE超疏水涂层	在超疏水涂层上的沉积速率仅为环氧硅树脂涂层的38.6%	—
3					EP/卵磷脂/SiO₂/HEDP	加入缓释填料后复合涂层的阻垢率高达80.7%，抗垢寿命是未添加磷脂包被填料涂层的2倍	耐腐蚀
4	CNTs^[6]				超疏水PFS-CNTs复合涂层	超疏水PFS- CNTs复合涂层上的结垢率仅为疏水PFS复合涂层的44%	—
5	TiO₂^[74]				含掺杂经全氟癸基三甲氧基硅烷改性的TiO₂粒子构建微纳米结构的超疏水涂层	涂层表面的结垢量分别减少了73.71%和55.38%	自清洁性
6	CeO₂^[58,68]				Cu-Zn-CeO₂协同防结垢涂层	管道钢表面有大量的菱面体CaCO₃，超亲水性Cu-Zn- CeO₂涂层上只出现了绒毛状文石	自清洁、防污
7	CeO₂^[58,68]				分层Ni-CeO₂涂层	Ni-CeO₂涂层（静态、动态）的缓蚀率均大于95%	耐酸碱性、自清洁性
8	CNTs^[26]	乳液聚合法	良好的分散性、高聚合速率、调节聚合物特性	反应难控制、依赖水相、	超疏水FEVE/FEP/CNTs/MC复合涂层	复合涂层的沉积速率仅为0.175mg/cm²（纯Al为1.81mg/cm²）	自修复、防污、抗冲击等
9	石墨及其衍生物^[38]	溶胶-凝胶法	易形成均匀纳米填料、可控性强、表面功能化	反应时间长、不易批量生产、	超疏水PPS/FKM/EG@SiO₂涂层	超疏水涂层CaCO₃垢沉积量为0.153mg/cm²，PPS/FKM（0.738mg/cm²）	自清洁、防污
10	TiO₂^[63]	溶胶-凝胶法	易形成均匀纳米填料、可控性强、表面功能化	反应时间长、不易批量生产、	超疏水/超亲油聚脲基复合涂层（FPUA@SiO₂/F-TWs）	与FPUA@SiO₂涂层相比，在水中结垢量增加4.2%（FPUA@SiO₂涂层为3.4%），在油中结垢量为5.08%	自清洁、防污、防腐、耐紫外线
11	TiO₂^[49]	氟化改性	改善表面性能、提高界面相容性和稳定性	成本高、工艺复杂	超疏水超亲油FEVE/PVDF/W-TiO₂/H-CNTs复合涂层	与FEVE/PVDF涂层相比（0.738mg/cm²），超疏水涂层表面CaCO₃沉积量减少0.451mg/cm²	自清洁、防污、耐久性
12	CNTs^[55]	氟化改性	改善表面性能、提高界面相容性和稳定性	成本高、工艺复杂	EP/iDCNTs/Zn/PVDF复合涂层	与EP涂层相比，复合涂层表面CaCO₃沉积量仅为EP的18.4%	耐腐蚀
13	TiO₂^[17-19,73]	水热合成法	均匀性好、成本低、环保、可控制填料的形态和性能	设备要求高、反应时间长、可能出现副反应	超疏水PVDF/FEVE/GO@TiO₂复合涂层	复合涂层的CaCO₃沉积量0.26mg/cm²（Al基质为0.44mg/cm²）	自清洁、防污、耐紫外线

序号	纳米填料	制备方法	优点	缺点	复合涂层	涂层性能	其他功能
1	纳米SiO₂^[6,47]	共混法	操作简单、适合大规模生产、适用多种基体材料，可灵活调控填料的种类、含量	分散性差、易团聚、填料与基体间界面相互作用弱	超疏水聚偏氟乙烯/氟化乙丙烯/二氧化硅（PFS）复合涂层	结垢率仅为疏水PFS复合涂层的44%	—
2					PPS/PTFE超疏水涂层	在超疏水涂层上的沉积速率仅为环氧硅树脂涂层的38.6%	—
3					EP/卵磷脂/SiO₂/HEDP	加入缓释填料后复合涂层的阻垢率高达80.7%，抗垢寿命是未添加磷脂包被填料涂层的2倍	耐腐蚀
4	CNTs^[6]				超疏水PFS-CNTs复合涂层	超疏水PFS- CNTs复合涂层上的结垢率仅为疏水PFS复合涂层的44%	—
5	TiO₂^[74]				含掺杂经全氟癸基三甲氧基硅烷改性的TiO₂粒子构建微纳米结构的超疏水涂层	涂层表面的结垢量分别减少了73.71%和55.38%	自清洁性
6	CeO₂^[58,68]				Cu-Zn-CeO₂协同防结垢涂层	管道钢表面有大量的菱面体CaCO₃，超亲水性Cu-Zn- CeO₂涂层上只出现了绒毛状文石	自清洁、防污
7	CeO₂^[58,68]				分层Ni-CeO₂涂层	Ni-CeO₂涂层（静态、动态）的缓蚀率均大于95%	耐酸碱性、自清洁性
8	CNTs^[26]	乳液聚合法	良好的分散性、高聚合速率、调节聚合物特性	反应难控制、依赖水相、	超疏水FEVE/FEP/CNTs/MC复合涂层	复合涂层的沉积速率仅为0.175mg/cm²（纯Al为1.81mg/cm²）	自修复、防污、抗冲击等
9	石墨及其衍生物^[38]	溶胶-凝胶法	易形成均匀纳米填料、可控性强、表面功能化	反应时间长、不易批量生产、	超疏水PPS/FKM/EG@SiO₂涂层	超疏水涂层CaCO₃垢沉积量为0.153mg/cm²，PPS/FKM（0.738mg/cm²）	自清洁、防污
10	TiO₂^[63]	溶胶-凝胶法	易形成均匀纳米填料、可控性强、表面功能化	反应时间长、不易批量生产、	超疏水/超亲油聚脲基复合涂层（FPUA@SiO₂/F-TWs）	与FPUA@SiO₂涂层相比，在水中结垢量增加4.2%（FPUA@SiO₂涂层为3.4%），在油中结垢量为5.08%	自清洁、防污、防腐、耐紫外线
11	TiO₂^[49]	氟化改性	改善表面性能、提高界面相容性和稳定性	成本高、工艺复杂	超疏水超亲油FEVE/PVDF/W-TiO₂/H-CNTs复合涂层	与FEVE/PVDF涂层相比（0.738mg/cm²），超疏水涂层表面CaCO₃沉积量减少0.451mg/cm²	自清洁、防污、耐久性
12	CNTs^[55]	氟化改性	改善表面性能、提高界面相容性和稳定性	成本高、工艺复杂	EP/iDCNTs/Zn/PVDF复合涂层	与EP涂层相比，复合涂层表面CaCO₃沉积量仅为EP的18.4%	耐腐蚀
13	TiO₂^[17-19,73]	水热合成法	均匀性好、成本低、环保、可控制填料的形态和性能	设备要求高、反应时间长、可能出现副反应	超疏水PVDF/FEVE/GO@TiO₂复合涂层	复合涂层的CaCO₃沉积量0.26mg/cm²（Al基质为0.44mg/cm²）	自清洁、防污、耐紫外线

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