基于烷基硫醇复合有机分子膜的制备及其对铜缓蚀性能的研究
发布时间：2018-11-04 16:31
【摘要】：铜及其合金是一种重要的结构和功能材料,因其具有良好的导热、导电性能和优美的外观而被广泛使用。但在酸性大气环境或离子浓度较高的溶液中,铜及其合金常因腐蚀介质的作用而发生腐蚀或变色,严重影响其使用性能和表观装饰性。因此,寻求高效、价廉便捷、绿色环保的铜防护技术具有重要的意义。自组装单分子膜(Self-assembled monolayers,SAMs)是活性分子通过化学键自发地吸附在异相界面上形成的具有一定取向、排列紧密的有序单层分子膜。自组装单分子膜制备条件温和、方法简单、且不改变基底材料的外观和内部性质,在金属腐蚀和防护领域有着广泛的应用前景。本论文中,我们在铜表面上制备了十八烷基硫醇的自组装单分子膜和复合有机分子膜。通过电化学测试、光谱技术、高分辨显微技术对硫醇单分子膜、硫醇与苯并三氮唑复合分子膜、硫醇与半胱氨酸复合分子膜的腐蚀防护性能进行了系统地研究,主要研究结果如下:(1)常温常压下,利用十八烷基硫醇(C_(18)SH)水溶液在铜表面上制备了C_(18)SH自组装单分子膜,并对C_(18)SH单分子膜的的缓蚀性能和作用机理进行了系统的研究。利用扫描电子显微镜观察铜试片盐水浸泡腐蚀后的形貌发现,C_(18)SH SAMs对铜具有良好的防腐蚀作用,修饰后的铜试样在腐蚀介质中长期稳定,表面无腐蚀现象。电化学测试结果表明表面覆盖C_(18)SH SAMs后,铜电极在Na Cl溶液中的伏安行为发生明显变化,阳极氧化电流峰几乎消失,阴极还原峰电流减小。C_(18)SH SAMs能够大幅提高电荷传递电阻,同时具有隔离金属基底与腐蚀介质的作用,对抑制铜的阳极溶解和溶解氧的阴极还原反应均有显著的抑制作用。延长组装时间和提高C_(18)SH的浓度有利于提高SAMs的缓蚀性能。此外,水溶液中C_(18)SH分子在铜表面的吸附是符合Langmuir吸附等温式的化学吸附过程。(2)采用苯并三氮唑(BTA)与烷基硫醇进行复配缓蚀,制备了BTA与C_(18)SH复合有机分子膜,研究了复合分子膜的防护性能和缓蚀作用机理,考察了配合方式、浓度对复配体系缓蚀效率的影响。腐蚀形貌表征与电化学测试结果表明,与单分子膜相比,复合分子膜的电子传递阻力更大,对电极反应的抑制作用更强烈,表现出良好的协同缓蚀效果。配合方式对复配体系的缓蚀效果有一定影响,其中同时吸附形成的BTA-C_(18)SH复合分子膜的缓蚀效果最佳,仅经过5 min浸泡处理其缓蚀效率可达99.87%。复合分子膜的缓蚀性能随BTA和C_(18)SH浓度的增大而提高。拉曼光谱和红外光谱结果表明复合分子膜中,BTA与C_(18)SH均通过去质子化共价吸附于铜表面。由于BTA的存在,C_(18)SH能够更好地维持原有的高密度堆积形态,复合分子膜的长期稳定性更好。(3)利用分子自组装技术在铜表面制备了半胱氨酸(L-Cys)单分子膜、L-Cys与C_(18)SH依次修饰的复合分子膜、L-Cys与C_(18)SH混合修饰的自组装膜,并研究三种有机分子膜的缓蚀性能及其影响因素。电化学测试结果表明,L-Cys SAMs在3.5 wt.%的Na Cl溶液中对铜基底具有较好的缓蚀效果,缓蚀效率随L-Cys浓度的增大而提高,并随组装时间的延长先小幅下降后提升。利用L-Cys对C_(18)SH SAMs进行两步法修饰所得的复合膜较单一分子膜耐蚀性有大幅提高。不同组合方式制备的复合分子膜的缓蚀效率略有差异,对此我们提出了相应的吸附模型。L-Cys与C_(18)SH混合自组装膜的膜层内分子堆积更致密,腐蚀通道更少,膜层在腐蚀介质中更稳定,表现出极佳的缓蚀性能。
[Abstract]:Copper and its alloys are an important structural and functional material which is widely used because of its good thermal conductivity, electrical conductivity and beautiful appearance. However, in solutions with higher acidic atmospheric environment or higher concentration of ions, copper and its alloys often corrode or discolor due to the action of corrosive medium, which seriously affects its performance and apparent decoration. Therefore, it is of great significance to seek high efficiency, cheap and convenient, green and environment-friendly copper protection technology. Self-assembly monomolecular film (SAMs) is an ordered monolayer molecule film with a certain orientation and tight alignment formed on the heterogeneous interface by self-assembly monomolecular film (SAMs). The self-assembled monomolecular film has the advantages of mild preparation condition, simple method and no change of the appearance and the internal property of the base material, and has wide application prospect in the field of fire protection and protection. In this paper, we prepared the self-assembled monolayer and composite organic molecular films of octadecylmercaptan on the surface of copper. The corrosion protection properties of thiol single-molecule membrane, thiol and benzene-and trinitrogen-linked composite molecular membrane, thiol and cysteine composite molecular membrane were systematically studied by electrochemical test, spectroscopy and high resolution microscopy. The main results are as follows: (1) normal temperature and normal pressure, C _ (18) SH self-assembled monolayer was prepared on the surface of copper using octadecylmercaptan (C _ (18) SH) aqueous solution, and the slow corrosion performance and mechanism of C _ (18) SH monomolecular film were studied systematically. It was found that C _ (18) SH SAMs have a good anti-corrosion effect on copper by scanning electron microscope, and the modified copper samples are stable in medium and long term, and the surface is free of corrosion. The electrochemical test results show that after the surface is covered with C _ (18) SH SAMs, the volt-ampere behavior of the copper electrode in the Na Cl solution is obviously changed, the anodic oxidation current peak disappears almost, and the cathodic reduction peak current decreases. C _ (18) SH SAMs can greatly improve the charge transfer resistance, but also has the effect of isolating the metal substrate and the corrosive medium, and has a remarkable inhibition effect on the cathodic reduction reaction of the anodic dissolution and the dissolved oxygen of the copper. prolonging the assembling time and increasing the concentration of C _ (18) SH is beneficial to improving the slow-etching performance of SAMs. In addition, the adsorption of C _ (18) SH molecules on the surface of copper in aqueous solution is consistent with the chemisorption process of Langmuir adsorption isotherm. (2) The compound organic molecular films of BTA and C _ (18) SH were prepared by compound slow corrosion of benzene and nitrogen trifluoride (BTA) and alkyl mercaptan, and the protective properties and corrosion mechanism of composite molecular films were studied. The results of corrosion morphology characterization and electrochemical test show that the electron transfer resistance of the composite molecular film is larger than that of the single molecule membrane, and the inhibition of the counter electrode reaction is stronger, showing a good synergistic effect. The slow erosion effect of BTA-C _ (18) SH composite molecular film formed at the same time is the best, which can reach 99. 87% only after 5 min soaking treatment. The corrosion resistance of the composite molecular film increases with the increase of BTA and C _ (18) SH concentration. Raman spectra and IR spectra show that both BTA and C _ (18) SH are covalently adsorbed on the surface of copper in the composite molecular film. Due to the existence of BTA, C _ (18) SH can better maintain the former high density bulk form, and the long-term stability of the composite molecular membrane is better. (3) Using the molecular self-assembly technique, a self-assembled monolayer of cysteine (L-lactide) monomolecular film, L-actin and C _ (18) SH were prepared on the surface of copper by molecular self-assembly technique, and the self-assembled monolayer modified by L-lactide and C _ (18) SH was prepared, and the slow corrosion performance and its influencing factors of the three organic molecular films were studied. The results of electrochemical tests indicate that the L-AlSAMs are in the range of 3. 5 wt. In the Na Cl solution of%, the copper substrate has a better slow corrosion effect, the slow corrosion efficiency increases with the increase of the L-Pb concentration, and decreases slightly after the extension of the assembly time. A two-step modification of C _ (18) SH SAMs by L-method has greatly improved the corrosion resistance of a single molecular film. The slow erosion efficiency of the composite molecular films prepared in different combinations is slightly different, and the corresponding adsorption model is proposed. The molecular accumulation of L-and C _ (18) SH mixed self-assembled films is more compact and less corrosive channels, and the film layers are more stable in corrosive medium, showing excellent corrosion resistance.
【学位授予单位】：湖南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TG174.46
本文编号：2310453
[Abstract]:Copper and its alloys are an important structural and functional material which is widely used because of its good thermal conductivity, electrical conductivity and beautiful appearance. However, in solutions with higher acidic atmospheric environment or higher concentration of ions, copper and its alloys often corrode or discolor due to the action of corrosive medium, which seriously affects its performance and apparent decoration. Therefore, it is of great significance to seek high efficiency, cheap and convenient, green and environment-friendly copper protection technology. Self-assembly monomolecular film (SAMs) is an ordered monolayer molecule film with a certain orientation and tight alignment formed on the heterogeneous interface by self-assembly monomolecular film (SAMs). The self-assembled monomolecular film has the advantages of mild preparation condition, simple method and no change of the appearance and the internal property of the base material, and has wide application prospect in the field of fire protection and protection. In this paper, we prepared the self-assembled monolayer and composite organic molecular films of octadecylmercaptan on the surface of copper. The corrosion protection properties of thiol single-molecule membrane, thiol and benzene-and trinitrogen-linked composite molecular membrane, thiol and cysteine composite molecular membrane were systematically studied by electrochemical test, spectroscopy and high resolution microscopy. The main results are as follows: (1) normal temperature and normal pressure, C _ (18) SH self-assembled monolayer was prepared on the surface of copper using octadecylmercaptan (C _ (18) SH) aqueous solution, and the slow corrosion performance and mechanism of C _ (18) SH monomolecular film were studied systematically. It was found that C _ (18) SH SAMs have a good anti-corrosion effect on copper by scanning electron microscope, and the modified copper samples are stable in medium and long term, and the surface is free of corrosion. The electrochemical test results show that after the surface is covered with C _ (18) SH SAMs, the volt-ampere behavior of the copper electrode in the Na Cl solution is obviously changed, the anodic oxidation current peak disappears almost, and the cathodic reduction peak current decreases. C _ (18) SH SAMs can greatly improve the charge transfer resistance, but also has the effect of isolating the metal substrate and the corrosive medium, and has a remarkable inhibition effect on the cathodic reduction reaction of the anodic dissolution and the dissolved oxygen of the copper. prolonging the assembling time and increasing the concentration of C _ (18) SH is beneficial to improving the slow-etching performance of SAMs. In addition, the adsorption of C _ (18) SH molecules on the surface of copper in aqueous solution is consistent with the chemisorption process of Langmuir adsorption isotherm. (2) The compound organic molecular films of BTA and C _ (18) SH were prepared by compound slow corrosion of benzene and nitrogen trifluoride (BTA) and alkyl mercaptan, and the protective properties and corrosion mechanism of composite molecular films were studied. The results of corrosion morphology characterization and electrochemical test show that the electron transfer resistance of the composite molecular film is larger than that of the single molecule membrane, and the inhibition of the counter electrode reaction is stronger, showing a good synergistic effect. The slow erosion effect of BTA-C _ (18) SH composite molecular film formed at the same time is the best, which can reach 99. 87% only after 5 min soaking treatment. The corrosion resistance of the composite molecular film increases with the increase of BTA and C _ (18) SH concentration. Raman spectra and IR spectra show that both BTA and C _ (18) SH are covalently adsorbed on the surface of copper in the composite molecular film. Due to the existence of BTA, C _ (18) SH can better maintain the former high density bulk form, and the long-term stability of the composite molecular membrane is better. (3) Using the molecular self-assembly technique, a self-assembled monolayer of cysteine (L-lactide) monomolecular film, L-actin and C _ (18) SH were prepared on the surface of copper by molecular self-assembly technique, and the self-assembled monolayer modified by L-lactide and C _ (18) SH was prepared, and the slow corrosion performance and its influencing factors of the three organic molecular films were studied. The results of electrochemical tests indicate that the L-AlSAMs are in the range of 3. 5 wt. In the Na Cl solution of%, the copper substrate has a better slow corrosion effect, the slow corrosion efficiency increases with the increase of the L-Pb concentration, and decreases slightly after the extension of the assembly time. A two-step modification of C _ (18) SH SAMs by L-method has greatly improved the corrosion resistance of a single molecular film. The slow erosion efficiency of the composite molecular films prepared in different combinations is slightly different, and the corresponding adsorption model is proposed. The molecular accumulation of L-and C _ (18) SH mixed self-assembled films is more compact and less corrosive channels, and the film layers are more stable in corrosive medium, showing excellent corrosion resistance.
【学位授予单位】：湖南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TG174.46
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