碳钢表面复合涂层的制备及在海水中的防腐性能研究
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摘要
随着碳钢材料越来越广泛的应用在海洋环境中,海洋环境中的防腐问题也受到了越来越多的重视。由于传统的防腐手段在海洋中的使用受到限制,且易造成严重的环境污染,因此研究方便,实用,经济,环保的新型海洋防腐材料成为当今的热门话题。
我们首先运用化学镀的方法在碳钢基底之上制备了Ni-P及不同PTFE颗粒含量的Ni-P-PTFE防腐镀层,并分别运用XRD、SEM、EDS、极化曲线和电化学阻抗等方法对其形貌、物相、组分和海水中的防腐性能进行了研究。结果表明:镀层的微观形貌随着镀层中PTFE颗粒含量的变化而产生巨大的差异。镀层的电化学防腐性能随着镀层中PTFE含量的增加明显降低,在镀液中只含有少量的PTFE乳液的情况(0.2mL/L),制备的镀层在海水中都具有最好的防腐性能,这归因于少量的PTFE颗粒的复合填充了镀层表面的细微孔洞。另外,海水灭菌处理对镀层的防腐性能也有一定的影响。
我们还设计运用溶胶-凝胶法制备TiO_2/ZnO复合陶瓷防腐涂层。在此之前,我们对涂层制备中使用的TiO_2/ZnO复合溶胶进行了后处理,并通过TG/DTA、XRD、SEM、HRTEM、FTIR、紫外吸收波谱等测试方法对得到的复合粉体的热稳定性、形貌、粒径、物相和光催化性能进行了探讨。结果显示:高温处理的TiO_2/ZnO复合粉体的结晶度得到了大幅度的提高,TiO_2也由锐钛矿相转化成了金红石相,并且在热处理过程中TiO_2和ZnO颗粒发生化学反应生成ZnTiO3相;经过氨水后处理的复合粉体,相的转变和化学反应一定程度上得到了抑制;复合粉体经过高温和NH3H2O处理后,光催化活性得到明显提高,这归因于粉体结晶度的提高、锐钛矿晶型的存在以及粉体平均粒径的减小。
在上述实验基础之上,我们在碳钢基底上制备TiO_2/ZnO复合陶瓷防腐涂层,并分别运用XRD、SEM、EDS、极化曲线、电化学阻抗等方法对其形貌、物相、组分和海水中的防腐性能进行了研究。实验结果显示:纯TiO_2涂层煅烧后会出现很多裂纹,而TiO_2/ZnO复合涂层热处理后表面致密,无明显裂纹。煅烧后基底会发生不同程度的氧化,且氧化物会与ZnO颗粒发生反应生成新的物质。TiO_2/ZnO复合涂层低温下防腐性能较差,其中纯TiO_2涂层的性能最差;而温度的升高对镀层的防腐性能有一定的提高作用。涂层厚度的增加也会提高防腐性能。
Nowadays, carbon steel has been widely used in the areas of sea, and the more attention is paid for the problem of corrosion for steel materials in the seawater. Because the traditional anticorrosion method was limited to use in environment of ocean, and was easy to cause severe environmental pollution, the study of new marine anticorrosive material with ability of convenient, practical, economic, environmental protection has become one of the hottest topics.
The Ni-P and Ni-P-PTFE coatings with various PTFE contents were electroless deposited on carbon steel and characterized through XRD, SEM, EDS, polarization curve and EIS. As a result, the microstructural morphologies of the coatings significantly varied with the PTFE content. The electrochemical anticorrosion capabilities of the coatings were seriously decreased with the increase of the PTFE content. The coating with a trace PTFE (PTFE emulsion concentration of 0.2mL/L in the plating bath) possessed excellent anticorrosion both in sterilized and unsterilized seawater which has been attributed to the absence of nano pores successfully blocked by the incorporated trace PTFE nano particles. Moreover, the process of sterilizing for seawater also affected the anticorrosion property of the coating.
Before preparing the TiO_2/ZnO composite coating by sol-gel process, the study on photocatalytic activity of powder from the TiO_2/ZnO composite sol was conducted. The as-prepared composite powder was characterized in detail using TGA, XRD, SEM, HRTEM and FTIR. The results showed that the particle crystallization of the composite powder was significantly promoted with the increase of the calcining temperature and the anatase was transformed to rutile during heating process. In addition, the reaction between TiO_2 and ZnO occurred when temperature increasing. However, the phase transformation and reaction mentioned above had been successfully retarded via the ammonia treating process. The particle crystallization of the composite powder was significantly promoted with the increase of the calcining temperature. The photocatalysis evaluation through MO degradation revealed an enhanced photocatalytic activity for the composite powder that might be related to the good crystallization, the presence of anatase phase, and the particle size reduction of the powder.
Then, the TiO_2/ZnO composite coatings were prepared on carbon steel via sol-gel process and the as-prepared coatings were characterized by XRD, SEM, EDS, polarization curve and EIS. The results showed that the TiO_2/ZnO composite coatings were more compact than pure TiO_2 coating. The matrix was oxidized after heating process and the reaction occurred between oxide and ZnO contained in coatings. The electrochemical anticorrosion capabilities of TiO_2/ZnO composite coatings varied with the heating temperature. The increasing for the thickness of coatings could improve the anticorrosion capabilities.
我们首先运用化学镀的方法在碳钢基底之上制备了Ni-P及不同PTFE颗粒含量的Ni-P-PTFE防腐镀层,并分别运用XRD、SEM、EDS、极化曲线和电化学阻抗等方法对其形貌、物相、组分和海水中的防腐性能进行了研究。结果表明:镀层的微观形貌随着镀层中PTFE颗粒含量的变化而产生巨大的差异。镀层的电化学防腐性能随着镀层中PTFE含量的增加明显降低,在镀液中只含有少量的PTFE乳液的情况(0.2mL/L),制备的镀层在海水中都具有最好的防腐性能,这归因于少量的PTFE颗粒的复合填充了镀层表面的细微孔洞。另外,海水灭菌处理对镀层的防腐性能也有一定的影响。
我们还设计运用溶胶-凝胶法制备TiO_2/ZnO复合陶瓷防腐涂层。在此之前,我们对涂层制备中使用的TiO_2/ZnO复合溶胶进行了后处理,并通过TG/DTA、XRD、SEM、HRTEM、FTIR、紫外吸收波谱等测试方法对得到的复合粉体的热稳定性、形貌、粒径、物相和光催化性能进行了探讨。结果显示:高温处理的TiO_2/ZnO复合粉体的结晶度得到了大幅度的提高,TiO_2也由锐钛矿相转化成了金红石相,并且在热处理过程中TiO_2和ZnO颗粒发生化学反应生成ZnTiO3相;经过氨水后处理的复合粉体,相的转变和化学反应一定程度上得到了抑制;复合粉体经过高温和NH3H2O处理后,光催化活性得到明显提高,这归因于粉体结晶度的提高、锐钛矿晶型的存在以及粉体平均粒径的减小。
在上述实验基础之上,我们在碳钢基底上制备TiO_2/ZnO复合陶瓷防腐涂层,并分别运用XRD、SEM、EDS、极化曲线、电化学阻抗等方法对其形貌、物相、组分和海水中的防腐性能进行了研究。实验结果显示:纯TiO_2涂层煅烧后会出现很多裂纹,而TiO_2/ZnO复合涂层热处理后表面致密,无明显裂纹。煅烧后基底会发生不同程度的氧化,且氧化物会与ZnO颗粒发生反应生成新的物质。TiO_2/ZnO复合涂层低温下防腐性能较差,其中纯TiO_2涂层的性能最差;而温度的升高对镀层的防腐性能有一定的提高作用。涂层厚度的增加也会提高防腐性能。
Nowadays, carbon steel has been widely used in the areas of sea, and the more attention is paid for the problem of corrosion for steel materials in the seawater. Because the traditional anticorrosion method was limited to use in environment of ocean, and was easy to cause severe environmental pollution, the study of new marine anticorrosive material with ability of convenient, practical, economic, environmental protection has become one of the hottest topics.
The Ni-P and Ni-P-PTFE coatings with various PTFE contents were electroless deposited on carbon steel and characterized through XRD, SEM, EDS, polarization curve and EIS. As a result, the microstructural morphologies of the coatings significantly varied with the PTFE content. The electrochemical anticorrosion capabilities of the coatings were seriously decreased with the increase of the PTFE content. The coating with a trace PTFE (PTFE emulsion concentration of 0.2mL/L in the plating bath) possessed excellent anticorrosion both in sterilized and unsterilized seawater which has been attributed to the absence of nano pores successfully blocked by the incorporated trace PTFE nano particles. Moreover, the process of sterilizing for seawater also affected the anticorrosion property of the coating.
Before preparing the TiO_2/ZnO composite coating by sol-gel process, the study on photocatalytic activity of powder from the TiO_2/ZnO composite sol was conducted. The as-prepared composite powder was characterized in detail using TGA, XRD, SEM, HRTEM and FTIR. The results showed that the particle crystallization of the composite powder was significantly promoted with the increase of the calcining temperature and the anatase was transformed to rutile during heating process. In addition, the reaction between TiO_2 and ZnO occurred when temperature increasing. However, the phase transformation and reaction mentioned above had been successfully retarded via the ammonia treating process. The particle crystallization of the composite powder was significantly promoted with the increase of the calcining temperature. The photocatalysis evaluation through MO degradation revealed an enhanced photocatalytic activity for the composite powder that might be related to the good crystallization, the presence of anatase phase, and the particle size reduction of the powder.
Then, the TiO_2/ZnO composite coatings were prepared on carbon steel via sol-gel process and the as-prepared coatings were characterized by XRD, SEM, EDS, polarization curve and EIS. The results showed that the TiO_2/ZnO composite coatings were more compact than pure TiO_2 coating. The matrix was oxidized after heating process and the reaction occurred between oxide and ZnO contained in coatings. The electrochemical anticorrosion capabilities of TiO_2/ZnO composite coatings varied with the heating temperature. The increasing for the thickness of coatings could improve the anticorrosion capabilities.
引文
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