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  本文關(guān)鍵詞：中性介質(zhì)中嘌呤衍生物抑制銅腐蝕的作用機(jī)制研究　出處：《山東大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 銅 緩蝕 電化學(xué)測量 SEM XPS 量子化學(xué)

【摘要】：銅具有良好的機(jī)械、力學(xué)、電學(xué)及耐蝕性能,在機(jī)械、國防、電力、化學(xué)等工業(yè)領(lǐng)域獲得了廣泛的應(yīng)用。但在某些環(huán)境下,如含氧的水、氧化性酸以及含Cl-、SO42-等離子的溶液中,銅依然會發(fā)生較嚴(yán)重腐蝕。添加緩蝕劑可以有效抑制銅的腐蝕,這種方法不改變金屬的物理化學(xué)性質(zhì),而且經(jīng)濟(jì)速效,操作簡便,在腐蝕防護(hù)領(lǐng)域得到廣泛的應(yīng)用。目前環(huán)境問題日益突出,人類環(huán)保意識逐漸增強(qiáng),對緩蝕劑的開發(fā)和應(yīng)用提出了新的要求,環(huán)境友好型緩蝕劑成為未來緩蝕劑的發(fā)展方向。嘌呤類物質(zhì)不僅含有豐富N和π鍵,而且毒性小,可生物降解,易于合成,價格低廉,對其作為緩蝕劑的研究具有重要意義。本論文用傳統(tǒng)電化學(xué)方法(動電位極化、電化學(xué)阻抗)輔以掃描電子顯微鏡研究了 0.5 M NaCl溶液和0.5 M Na2S04溶液中6-芐氨基嘌呤(6-BA)、6-氯鳥嘌呤(6-CG)、6-巰基嘌呤(6-MP)和腺嘌呤(AD)等四種嘌f$衍生物對銅腐蝕的抑制作用,分析了不同取代基對緩蝕性能的影響并討論了原因。借助X射線光電子能譜分析了試樣表面化學(xué)組成,提出了緩蝕劑吸附模型。用量子化學(xué)理論確定了緩蝕劑潛在吸附位點,分析了緩蝕性能與量子化學(xué)參數(shù)的關(guān)系。主要工作如下:1.電化學(xué)測試采用傳統(tǒng)電化學(xué)方法(動電位極化、電化學(xué)阻抗)研究了 0.5 MNaCl溶液和0.5 MNa2S04溶液中6-BA、6-CG、6-MP和AD對銅的緩蝕作用,結(jié)果表明,這四種嘌呤衍生物均有良好的緩蝕性能。動電位極化實驗結(jié)果顯示,6-BA、6-CG、6-MP和AD同時明顯降低了陰陽極的腐蝕電流密度,屬于混合型緩蝕劑。電化學(xué)阻抗實驗結(jié)果表明,這四種物質(zhì)增加了表面膜的穩(wěn)定性,抑制了銅的腐蝕。2.熱力學(xué)計算進(jìn)行0.5 MNaCl溶液中AD在銅表面的吸附等溫式擬合,結(jié)果顯示,該條件下AD的吸附符合Langmuir吸附等溫式模型,是自發(fā)的過程,且物理吸附和化學(xué)吸附共同作用。3.表面形貌分析用SEM觀察表面形貌并進(jìn)行對比分析。結(jié)果發(fā)現(xiàn),未添加緩蝕劑的試樣表面發(fā)生了明顯的全面腐蝕,產(chǎn)生了許多腐蝕產(chǎn)物,表面變得非常粗糙。而添加緩蝕劑的試樣腐蝕輕微,表面有少量的腐蝕產(chǎn)物。說明緩蝕劑能夠在銅表面成膜,抑制了銅的腐蝕。4.表面元素檢測銅試樣表面元素用XPS進(jìn)行測試。全譜掃描結(jié)果顯示,浸泡后試樣表面有N,證明了緩蝕劑的存在。窄區(qū)掃描得到了試樣表面的化學(xué)組成。此外,根據(jù)元素的化學(xué)位移,推測出了緩蝕劑的吸附模式,提出了吸附模型:6-CG和AD以平鋪的形式吸附在銅表面;6-BA的嘌呤基體和氨基部分也是以平鋪的形式吸附,但是芐基部分沒有吸附,而是伸入到腐蝕介質(zhì)中;6-MP通過S和咪唑環(huán)內(nèi)-N=以一定角度吸附在銅表面。5.量子化學(xué)計算采用密度泛函理論(DFT),在6-311+G(d)基組下,通過Gaussian 03程序進(jìn)行所有原子的理論計算,得到了相關(guān)的量子化學(xué)參數(shù):分子優(yōu)化結(jié)構(gòu)及其骨架原子的Mulliken電荷分布、最高占據(jù)分子軌道能量(EHOMO)、最低未占據(jù)分子軌道能量(ELUMO)、能量差(△E)、分子偶極矩(μ)和電子轉(zhuǎn)移數(shù)(△N)。確定了潛在的吸附位點,分析了緩蝕性能與量子化學(xué)參數(shù)的關(guān)系。
[Abstract]:Copper has good mechanical, electrical and mechanical, corrosion resistance, mechanical, defense, power, chemical and other industries has been widely used. But in some circumstances, such as oxygen and water, oxidizing acid solution containing Cl-, SO42- plasma, copper still had more serious corrosion to add. The corrosion inhibitor can effectively inhibit the copper, this method does not change the physical and chemical properties of metals, and the economy is quick, simple, widely used in corrosion protection field. At present, environmental problems have become increasingly prominent, the human environmental protection consciousness strengthens gradually, put forward new requirements for the development and application of corrosion inhibitor, environment friendly type inhibitor has become the future development direction of the inhibitor. The purine compounds not only rich in N and pi bond, and has little toxicity, biodegradable, easy synthesis, low price, is of great significance to the study as a corrosion inhibitor on this. The traditional electrochemical methods (potentiodynamic polarization, electrochemical impedance spectroscopy) and scanning electron microscopy studies 6- 6-Benzylaminopurine 0.5 M NaCl solution and 0.5 M Na2S04 solution (6-BA), 6- chloride (6-CG), guanine 6- mercaptopurine (6-MP) and adenine (AD) inhibitory effect of four kinds of purine derivatives on f$copper corrosion, analysis of different substituent effect on corrosion inhibition performance and discuss the reasons. By means of X ray photoelectron spectrum analysis of the chemical composition of sample surface, the corrosion inhibitor corrosion inhibitor adsorption model. The potential adsorption sites determined by quantum chemistry theory, analyzes the relationship between the inhibition efficiency and quantum chemical parameters the main work is as follows: 1. the traditional electrochemical methods (by electrochemical potentiodynamic polarization, electrochemical impedance) of 6-CG 6-BA, 0.5 MNaCl and 0.5 MNa2S04 solutions, 6-MP and AD on the corrosion inhibition of copper used, results show that the four. Good corrosion inhibition performance in derivatives possess potentiodynamic polarization. The experimental results show that 6-BA, 6-CG, 6-MP and AD also significantly decreased the corrosion current density of cathode and anode, belongs to mixed type inhibitor. The electrochemical impedance experiments show that these four substances increase stability of the surface film, inhibiting corrosion thermodynamics.2. the calculation of copper in 0.5 MNaCl solution for AD display results in adsorption isotherm fitting, the copper surface, the adsorption of AD under the Langmuir adsorption isotherm model, is a spontaneous process, and physical adsorption and chemical adsorption with SEM to observe the surface morphology and comparative analysis of the interaction of.3. surface morphology analysis. The results showed that the surface of the sample without obvious comprehensive corrosion inhibitor, produced a lot of corrosion products, surface to become very rough. And the corrosion inhibitor added slightly, a small amount of surface corrosion products At that the inhibitor in the film surface of copper, inhibiting corrosion of.4. surface element copper copper specimen surface element detection was tested using XPS. Full spectrum scanning showed that the surface of the sample after soaking N, proved that the corrosion inhibitor. The chemical composition of the narrow area of the scanning surface. In addition according to the chemical displacement, element, deduced that the adsorption model of corrosion inhibitor, adsorption models were proposed: 6-CG and AD in the form of tile adsorbed on the copper surface; purine substrate and part of 6-BA is in the form of amino acid adsorption tile, but not part of benzyl adsorption, but extends into the corrosive medium; 6-MP by S -N= and imidazole ring at a certain angle adsorbed on the copper surface.5. quantum chemical calculations using density functional theory (DFT), 6-311+G (d) group, through the Gaussian 03 program for all atoms of theoretical calculation of quantum chemistry has been related. Number: Mulliken molecular charge distribution to optimize the structure and skeleton of the atom, the highest occupied molecular orbital energy (EHOMO), the lowest unoccupied molecular orbital energy (ELUMO), the energy difference (delta E), dipole moment (U) and electron transfer (N). To determine the adsorption potential sites, analysis the relationship between inhibition efficiency and quantum chemical parameters.

【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TG174.42

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