含氮杂环有机青铜缓蚀剂的缓蚀性能及其机理研究
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摘要
青铜文物是我国古代文明的象征之一,具有极高的历史、艺术和科学价值。由于埋藏时间长及出土后存贮条件的改变等原因,使古代青铜器面临着严峻的腐蚀防护问题。青铜器在潮湿、含有氯离子及氧化性气氛环境里,容易发生一种危害性极大、被称之为“青铜病”的腐蚀过程,使青铜文物受到严重的损害。
使用和添加缓蚀剂已成为防腐蚀技术中应用最为广泛的方法之一。其中有机型缓蚀剂具有良好的缓蚀效果和较高的经济效益,成为缓蚀剂研究的热点。大量研究表明:有机型缓蚀剂可以通过其杂环原子,如O、N、S、P,或者不饱和键与金属表面吸附,达到抑制腐蚀的效果。基于以上观点,一些唑类化合物被用作青铜缓蚀剂,发挥其防腐蚀的作用。尽管如此,对含氮杂环有机化合物的缓蚀作用机理却有待改善。本论文发展了三种含氮有机杂环化合物的缓蚀机理,并对其进行缓蚀性能评价。
本论文筛选了3种含氮杂环有机缓蚀剂BTA(苯并三唑,Benzotriazole)、AMT(2-氨基-5-巯基-1,3,4-噻二唑)和MBO(2-巯基苯并恶唑),通过失重试验、表面分析、X射线衍射和傅里叶红外光谱仪等多种手段和方法测试了其缓蚀性能,分析了它们对青铜的缓蚀机理,从理论上探讨了缓蚀剂分子与金属表面的作用方式,归纳了分子结构与缓蚀效果之间的关系。主要结论如下:
酸性介质中的失重实验表明,青铜在盐酸介质中的缓蚀效率依次为MBO>AMT>BTA。在柠檬酸介质中,由于AMT在青铜表面形成保护膜,其缓蚀效率达到100%,高于MBO及BTA。
对除锈前后的青铜试片的扫描电镜观察表明,经BTA处理的青铜试片表面存在较大孔隙的防护膜,而经AMT处理的青铜试片表面形成有较紧密的防护膜。经MBO处理的青铜试片表面膜形貌呈颗粒状分布,其表面不够紧密。
X射线衍射和傅里叶红外光谱结果都证实,BTA处理后的反应产物为Cu(I)-BTA,AMT与铜锈的反应产物有Cu(Ⅱ)-AMT和Cu(I)-AMT,MBO处理后的反应产物为Cu(I)-MBO。
Bronze relics with high historical, artistic and scientific value are one of the symbolizations of ancient civilization of human being. Due to their long buried time, changes of the storage condition after excavation etc., it is a great challenge for us to take measures to prevent the ancient bronze relics from corrosion. Bronze in the wet, containing chloride ions and oxidizing atmosphere environment, prone to a great danger of being referred to as“bronze disease”of the corrosion process, so that bronze objects were seriously damage.
The use of inhibitors is one of the most practical methods for protection against corrosion. Numerous researches on corrosion inhibition using organic compounds have been reported due to its highly efficient and cost-effective. It has been accepted that most organic compounds employed as corrosion inhibitors can adsorb on the metal surface through heteroatoms such as nitrogen,sulfur,oxygen,phosphorus and multiple bonds etc preventing steel from corrosion. Based on the conclusions, azole compounds are a number of bronze used as a corrosion inhibitor, to play its role in anti-corrosion. However, the corrosion inhibiting mechanism of the N-heterocyclic organic compounds compounds is not so clear. The aim of this work is to obtain a better understanding of the inhibiting behaviour of the N-heterocyclic organic compounds compounds derivatives and predict corrosion efficiency of similar structures in order to design compounds for testing their corrosion inhibition.
N-heterocyclic organic inhibitors involved in this paper and the inhibiting performance of these derivatives was evaluated by weight loss, scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) testing. The corrosion inhibiting mechanism of these derivatives and the relationship between the bronze structure and their inhibiting efficiency were discussed. The following conclusions may be drawn:
The weight loss experiments in the acid medium for 10 hours have demonstrated that the inhibition efficiency in hydrochloric acid medium is MBO> AMT> BTA. The inhibition efficiency of the AMT in the citric acid solution is 100%, higher than that of MBO and BTA because a protective film is formed on the surface of AMT treated bronze in the the citric acid solution.
SEM observation showed that the film formed on the surface of the BTA treated rust bronze is loose while the surface of the AMT processed patina bronze samples has a dense protection film. The surface morphology of MBO processed bronze samples is much looser than that of BTA processed bronze samples.
X-ray diffraction and FTIR results confirmed that after BTA and MBO treatment, the reaction products on the surface of bronze is Cu(I)-BTA and Cu(I)-MBO, respectively, while after the AMT treatment, there is a product of Bellamya reaction Cu (Ⅱ)-AMT and Cu (I)-AMT on the surface of bronze.
使用和添加缓蚀剂已成为防腐蚀技术中应用最为广泛的方法之一。其中有机型缓蚀剂具有良好的缓蚀效果和较高的经济效益,成为缓蚀剂研究的热点。大量研究表明:有机型缓蚀剂可以通过其杂环原子,如O、N、S、P,或者不饱和键与金属表面吸附,达到抑制腐蚀的效果。基于以上观点,一些唑类化合物被用作青铜缓蚀剂,发挥其防腐蚀的作用。尽管如此,对含氮杂环有机化合物的缓蚀作用机理却有待改善。本论文发展了三种含氮有机杂环化合物的缓蚀机理,并对其进行缓蚀性能评价。
本论文筛选了3种含氮杂环有机缓蚀剂BTA(苯并三唑,Benzotriazole)、AMT(2-氨基-5-巯基-1,3,4-噻二唑)和MBO(2-巯基苯并恶唑),通过失重试验、表面分析、X射线衍射和傅里叶红外光谱仪等多种手段和方法测试了其缓蚀性能,分析了它们对青铜的缓蚀机理,从理论上探讨了缓蚀剂分子与金属表面的作用方式,归纳了分子结构与缓蚀效果之间的关系。主要结论如下:
酸性介质中的失重实验表明,青铜在盐酸介质中的缓蚀效率依次为MBO>AMT>BTA。在柠檬酸介质中,由于AMT在青铜表面形成保护膜,其缓蚀效率达到100%,高于MBO及BTA。
对除锈前后的青铜试片的扫描电镜观察表明,经BTA处理的青铜试片表面存在较大孔隙的防护膜,而经AMT处理的青铜试片表面形成有较紧密的防护膜。经MBO处理的青铜试片表面膜形貌呈颗粒状分布,其表面不够紧密。
X射线衍射和傅里叶红外光谱结果都证实,BTA处理后的反应产物为Cu(I)-BTA,AMT与铜锈的反应产物有Cu(Ⅱ)-AMT和Cu(I)-AMT,MBO处理后的反应产物为Cu(I)-MBO。
Bronze relics with high historical, artistic and scientific value are one of the symbolizations of ancient civilization of human being. Due to their long buried time, changes of the storage condition after excavation etc., it is a great challenge for us to take measures to prevent the ancient bronze relics from corrosion. Bronze in the wet, containing chloride ions and oxidizing atmosphere environment, prone to a great danger of being referred to as“bronze disease”of the corrosion process, so that bronze objects were seriously damage.
The use of inhibitors is one of the most practical methods for protection against corrosion. Numerous researches on corrosion inhibition using organic compounds have been reported due to its highly efficient and cost-effective. It has been accepted that most organic compounds employed as corrosion inhibitors can adsorb on the metal surface through heteroatoms such as nitrogen,sulfur,oxygen,phosphorus and multiple bonds etc preventing steel from corrosion. Based on the conclusions, azole compounds are a number of bronze used as a corrosion inhibitor, to play its role in anti-corrosion. However, the corrosion inhibiting mechanism of the N-heterocyclic organic compounds compounds is not so clear. The aim of this work is to obtain a better understanding of the inhibiting behaviour of the N-heterocyclic organic compounds compounds derivatives and predict corrosion efficiency of similar structures in order to design compounds for testing their corrosion inhibition.
N-heterocyclic organic inhibitors involved in this paper and the inhibiting performance of these derivatives was evaluated by weight loss, scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) testing. The corrosion inhibiting mechanism of these derivatives and the relationship between the bronze structure and their inhibiting efficiency were discussed. The following conclusions may be drawn:
The weight loss experiments in the acid medium for 10 hours have demonstrated that the inhibition efficiency in hydrochloric acid medium is MBO> AMT> BTA. The inhibition efficiency of the AMT in the citric acid solution is 100%, higher than that of MBO and BTA because a protective film is formed on the surface of AMT treated bronze in the the citric acid solution.
SEM observation showed that the film formed on the surface of the BTA treated rust bronze is loose while the surface of the AMT processed patina bronze samples has a dense protection film. The surface morphology of MBO processed bronze samples is much looser than that of BTA processed bronze samples.
X-ray diffraction and FTIR results confirmed that after BTA and MBO treatment, the reaction products on the surface of bronze is Cu(I)-BTA and Cu(I)-MBO, respectively, while after the AMT treatment, there is a product of Bellamya reaction Cu (Ⅱ)-AMT and Cu (I)-AMT on the surface of bronze.
引文
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