【作者】 李勇；

【导师】 向斌；

【作者基本信息】 重庆大学 ， 工程（化学工程）（专业学位）， 2022， 硕士

【摘要】 随着中国制造业和建筑业快速发展,铜的应用更加广泛和普遍,我国对铜的需求日益显著。但铜在一些恶劣环境下,会发生较为严重的腐蚀,导致资源浪费、生产效率降低等问题,造成一系列经济损失或安全问题。为此,金属铜的腐蚀和防护引起了广泛的关注和研究。其中,缓蚀剂防腐技术具有高效快捷、可操作性强、设备简单等优点,在金属防腐蚀领域具有良好的应用前景。由于传统缓蚀剂的毒性普遍较大,随着绿色化学的发展和人们环保意识的不断提高,绿色高效腐蚀抑制剂的开发和探索已成为当前的重要课题。近年来,临床上的一些药物被研究用作缓蚀剂,实验证实了它们在酸性溶液中表现出优异的防腐蚀性能。本论文选取了七种毒性较低、价格便宜,且具有较好溶解性的哌嗪衍生物类药物作缓蚀剂。七种药物分别为氟奋乃静（FPZ）、三氟拉嗪（TPZ）、阿莫沙平（AP）、洛沙平（LP）、氯氮平（CP）、喹硫平（QTP）和11-（1-哌嗪基）二苯并[B,F][1,4]硫氮杂卓（11-PDTP）。通过系统的电化学测试和形貌表征等方法深入探讨了七种药物缓蚀剂分子的性能和机理,并通过理论计算,从分子/原子尺度上研究了缓蚀剂分子对铜表面防护机制,为发展绿色、高效、新型的缓蚀剂提供了实验和理论指导。本文研究内容如下:（1）通过电化学测试表明,在0.5 M硫酸溶液中,FPZ和TPZ对铜具有良好的缓蚀性能,两者均属于阴极型缓蚀剂,且FPZ比TPZ具有更好的缓蚀性能,对实验前后的样品进行了形貌分析。傅里叶变换红外光谱（FT-IR）进一步证实了这两种化合物能够与铜形成配位键。X射线光电子能谱（XPS）证实,这两种缓蚀剂主要依靠N和S原子作为活性基团在Cu表面实现吸附。理论计算表明FPZ中的-CH₃能够提供电子,增强缓蚀性能,而TPZ上的-OH具有吸电子的诱导作用,不能延缓腐蚀,因此,FPZ的缓蚀性能要好于TPZ。此外,FPZ和TPZ在Cu表面的吸附符合Langmuir等温模型。（2）通过电化学测试,AP、LP和CP均在添加浓度为5 m M时的缓蚀效率最高,分别为94.0%、95.2%和96.6%,且都是阴极型缓蚀剂。形貌分析表明,缓蚀剂能够在铜表面形成一层致密的保护膜。AP、LP和CP在Cu表面的吸收符合Langmuir等温模型。理论计算揭示了其吸附模型和防腐机理,同时证明了由于LP中甲基供电子作用增强了与之相连苯环的共轭效应,因此LP的缓蚀性能好于AP。（3）通过电化学实验和表面形貌分析等方法,研究了不同结构的QTP和11-PDTP对铜在0.5 M硫酸溶液中的缓蚀性能和缓蚀机理。从实验和理论计算结果可知,两种缓蚀剂的电子云主要分布在类吩噻嗪环上,由于空间位阻效应,使哌嗪环与铜表面成一定的角度而远离,且QTP由于其复杂的长支链进一步增大空间位阻导致斥力更大,从而降低其对铜的吸附能力。因此11-PDTP的缓蚀性能优于QTP。更多还原

【Abstract】 While the rapid development of China’s manufacturing and construction industries,as well as the proposition of"Made in China-2025",the application of copper is more extensive and common,and the demand for copper is increasingly significant in China.However,in some harsh environments,the corrosion of copper will be more serious,resulting in a series of economic losses or safety problems such as the waste of resources and reduction of production efficiency.Therefore,the corrosion and anticorrosion of metallic copper has attracted extensive attention and study.Among them,the anticorrosion technology of corrosion inhibitors has the advantages of high efficiency,high operability,using simple equipment,etc.,owing great application prospect in the field of metal anticorrosion.Due to the generally high toxicity of traditional corrosion inhibitors,with the development of green chemistry and the continuous improvement of people’s awareness toward environmental protection,the development and exploration of green and highly efficient corrosion inhibitors has become an important research topic at present.In recent years,seven clinical drugs have been studied as corrosion inhibitors,and experiments have confirmed their excellent anti-corrosion properties in acidic solutions.In this paper,seven piperazine derivatives drugs,which can be taken orally with low toxicity,cheap price,and good solubility,are selected as anti-corrosive agents.The seven drugs include Flufen azine（FPZ）,Trifluoperazine（TPZ）,Amoxapine（AP）,Loxapine（L）,Clozapine（CP）,Quetiapine（QTP）and 11-（1-Piperazine）-dibenzo[b,f][1,4]thiazepine dihydrochloride（11-PDTP）.The properties and mechanisms of the seven corrosion inhibitor molecules are studied by systematic electrochemical testing,morphology characterization and etc.Besides,the protection mechanism on copper surface worked by anti-corrosive molecules are discussed on molecular/atomic scale through theoretical calculation.These studies provide experimental and theoretical guidance for developing green,highly efficient and new corrosion inhibitors.The research contents of this paper are as follows:（1）The electrochemical measurements signify the favorable properties of FPZ and TPZ in resisting Cu corrosion in 0.5M H₂SO₄.Both of them belong to cathodic-type corrosion inhibitors,and FPZ possess more excellent anti-corrosive capacity than TPZ.Morphology analysis shows that the two corrosion inhibitors have excellent corrosion inhibition performance.The Fourier transform infrared spectroscopy（FT-IR）further attest that the two compounds can form coordination bonds with copper.The two inhibitors mainly depend on the N and S atoms as active groups to adsorb on Cu surface which was confirmed by X-ray photoelectron spectroscopy（XPS）.Theoretical calculation shows that-CH₃ in FPZ can provide electrons and enhance corrosion inhibition performance,while-OH on TPZ can induce electrons and cannot delay corrosion.Additionally,the adsorption of FPZ and TPZ on Cu surface defer to the Langmuir isotherm model.（2）According to the electrochemical results,the anti-corrosion efficiencies of AP,LP and CP reached their maximums at 5 m M,namely 94.0%,95.2%and 96.6%,respectively.They are all proved to be cathodic-type corrosion inhibitors.The morphology analysis imply the shaping of densely protective films on Cu surfaces.Moreover,the absorption of AP、LP and CP on Cu surfaces defer to the Langmuir isotherm model.Theoretical calculations reveal its adsorption model and anti-corrosion mechanism,demonstrating that the methyl group attach to the benzene ring can enhance the anti-corrosive efficiency due to its promoting the conjugation effect.So the corrosion inhibition performance of LP is better than AP.（3）By means of electrochemical experiments and surface morphology analysis,the anti-corrosive properties and mechanism of QTP and 11-PDTP were investigated for copper in 0.5 M H₂SO₄.According to the experimental and theoretical calculation results,it is clear that the electron clouds of the two inhibitors are mainly distributed on the phenothiazine ring.Piperazine ring is at a certain angle to the copper surface due to steric hindrance effect.Besides,because of the complex long branched chain,QTP owns larger repulsive force caused by steric hindrance,which reduced the adsorption ability on copper.Thus,the anti-corrosive performance of 11-PDTP is better than that of QTP.更多还原