硫酸二次掺杂聚苯胺/石墨烯/碳纳米管复合材料制备及其防腐性能

Preparation and anti-corrosion properties of sulfuric acid secondary doped polyaniline/graphene/carbon nanotube composites

  • 摘要: 为改善纳米复合材料形貌结构和提高其防腐性能,减少材料腐蚀导致的经济损失和安全事故,本文在硫酸体系中通过原位聚合将苯胺(ANI)分别与不同配比的还原氧化石墨烯(RGO)和碳纳米管(CNTs)制备RGO/PANI和CNTs/PANI一次掺杂态产物,将一次掺杂态产物分别经氨水解掺杂后,在硫酸体系中对两种产物共同进行二次掺杂制备得到硫酸RGO CNTs/Redoped PANI复合材料。采用SEM、TEM、FTIR、UV-Vis对不同产物的形貌和结构进行表征,通过电化学测试研究了产物的防腐性能;并将二次掺杂制备的三元纳米复合材料与环氧树脂制备成涂层,对涂层进行交流阻抗测试和中性盐雾试验。结果表明:二次掺杂方法可有效提升原位聚合的产物性能;在RGO∶ANI为1∶10、CNTs∶ANI为1∶15时,产物形貌和防腐性能最优,缓蚀率可达81.18%;制备的复合涂层在3.5wt% NaCl溶液中浸泡1440 h后,仍保持较高阻抗值,添加量为1wt%的涂层阻抗值达6.019×1010 Ω·cm2,且经1440 h中性盐雾试验后,涂层表面无鼓泡和其他劣化现象,仅在划痕处有少量锈蚀但未扩散蔓延,体现出优异的防腐性能。表明开发基于聚苯胺纳米复合材料重防腐涂料体系的可行性,可为金属材料提供长效防护。

     

    Abstract: In order to improve the morphology and structure of nanocomposites, improve their anti-corrosion properties, and reduce the economic losses and safety accidents caused by material corrosion, aniline (ANI) was combined with different ratios of graphene (RGO) and carbon nanotubes (CNTs) to synthesize RGO/polyaniline (PANI) primary doped products and CNTs/PANI primary doped products. After redoping with ammonia, the RGO CNTs/redoped PANI composite were prepared by secondary doping of the two products in the sulfuric acid system. The morphology and structure of different PANI products were characterized by means of scanning electron microscopy, transmission electron microscopy. The anti-corrosion properties of different products were tested by electrochemical workstation, the best performing PANI composite material was combined with resin to prepare PANI epoxy coating. Anticorrosive properties of the coatings soaked for a long time were studied by AC impedance test and verified by neutral salt spray test. The performances of the composite materials prepared by secondary doping alone are significantly improved compared to those prepared by direct blending, the product has the best morphology and anti-corrosion performance when RGO∶ANI is 1∶10 and CNTs∶ANI is 1∶15, with the corrosion inhibition rate of 81.18%, the PANI epoxy coatings still exhibit high impedance values after soaking in 3.5wt% NaCl solution for 1440 h, with the highest impedance value reaching 6.019×1010 Ω·cm2 when the PANI addition amount is 1wt%, and there is no obvious corrosion on the coating surface after 1440 h neutral salt spray test, the coating surface has no bubbling and other deterioration phenomena, only a small amount of rust in the scratch but not spread, reflecting excellent anti-corrosion properties. It is feasible to develop a heavy anticorrosive coating system based on polyaniline nanocomposites, which can provide long-term protection for metal materials.

     

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