基于烷基硫醇復(fù)合有機(jī)分子膜的制備及其對(duì)銅緩蝕性能的研究
發(fā)布時(shí)間：2018-11-04 16:31
【摘要】：銅及其合金是一種重要的結(jié)構(gòu)和功能材料,因其具有良好的導(dǎo)熱、導(dǎo)電性能和優(yōu)美的外觀而被廣泛使用。但在酸性大氣環(huán)境或離子濃度較高的溶液中,銅及其合金常因腐蝕介質(zhì)的作用而發(fā)生腐蝕或變色,嚴(yán)重影響其使用性能和表觀裝飾性。因此,尋求高效、價(jià)廉便捷、綠色環(huán)保的銅防護(hù)技術(shù)具有重要的意義。自組裝單分子膜(Self-assembled monolayers,SAMs)是活性分子通過化學(xué)鍵自發(fā)地吸附在異相界面上形成的具有一定取向、排列緊密的有序單層分子膜。自組裝單分子膜制備條件溫和、方法簡單、且不改變基底材料的外觀和內(nèi)部性質(zhì),在金屬腐蝕和防護(hù)領(lǐng)域有著廣泛的應(yīng)用前景。本論文中,我們在銅表面上制備了十八烷基硫醇的自組裝單分子膜和復(fù)合有機(jī)分子膜。通過電化學(xué)測試、光譜技術(shù)、高分辨顯微技術(shù)對(duì)硫醇單分子膜、硫醇與苯并三氮唑復(fù)合分子膜、硫醇與半胱氨酸復(fù)合分子膜的腐蝕防護(hù)性能進(jìn)行了系統(tǒng)地研究,主要研究結(jié)果如下:(1)常溫常壓下,利用十八烷基硫醇(C_(18)SH)水溶液在銅表面上制備了C_(18)SH自組裝單分子膜,并對(duì)C_(18)SH單分子膜的的緩蝕性能和作用機(jī)理進(jìn)行了系統(tǒng)的研究。利用掃描電子顯微鏡觀察銅試片鹽水浸泡腐蝕后的形貌發(fā)現(xiàn),C_(18)SH SAMs對(duì)銅具有良好的防腐蝕作用,修飾后的銅試樣在腐蝕介質(zhì)中長期穩(wěn)定,表面無腐蝕現(xiàn)象。電化學(xué)測試結(jié)果表明表面覆蓋C_(18)SH SAMs后,銅電極在Na Cl溶液中的伏安行為發(fā)生明顯變化,陽極氧化電流峰幾乎消失,陰極還原峰電流減小。C_(18)SH SAMs能夠大幅提高電荷傳遞電阻,同時(shí)具有隔離金屬基底與腐蝕介質(zhì)的作用,對(duì)抑制銅的陽極溶解和溶解氧的陰極還原反應(yīng)均有顯著的抑制作用。延長組裝時(shí)間和提高C_(18)SH的濃度有利于提高SAMs的緩蝕性能。此外,水溶液中C_(18)SH分子在銅表面的吸附是符合Langmuir吸附等溫式的化學(xué)吸附過程。(2)采用苯并三氮唑(BTA)與烷基硫醇進(jìn)行復(fù)配緩蝕,制備了BTA與C_(18)SH復(fù)合有機(jī)分子膜,研究了復(fù)合分子膜的防護(hù)性能和緩蝕作用機(jī)理,考察了配合方式、濃度對(duì)復(fù)配體系緩蝕效率的影響。腐蝕形貌表征與電化學(xué)測試結(jié)果表明,與單分子膜相比,復(fù)合分子膜的電子傳遞阻力更大,對(duì)電極反應(yīng)的抑制作用更強(qiáng)烈,表現(xiàn)出良好的協(xié)同緩蝕效果。配合方式對(duì)復(fù)配體系的緩蝕效果有一定影響,其中同時(shí)吸附形成的BTA-C_(18)SH復(fù)合分子膜的緩蝕效果最佳,僅經(jīng)過5 min浸泡處理其緩蝕效率可達(dá)99.87%。復(fù)合分子膜的緩蝕性能隨BTA和C_(18)SH濃度的增大而提高。拉曼光譜和紅外光譜結(jié)果表明復(fù)合分子膜中,BTA與C_(18)SH均通過去質(zhì)子化共價(jià)吸附于銅表面。由于BTA的存在,C_(18)SH能夠更好地維持原有的高密度堆積形態(tài),復(fù)合分子膜的長期穩(wěn)定性更好。(3)利用分子自組裝技術(shù)在銅表面制備了半胱氨酸(L-Cys)單分子膜、L-Cys與C_(18)SH依次修飾的復(fù)合分子膜、L-Cys與C_(18)SH混合修飾的自組裝膜,并研究三種有機(jī)分子膜的緩蝕性能及其影響因素。電化學(xué)測試結(jié)果表明,L-Cys SAMs在3.5 wt.%的Na Cl溶液中對(duì)銅基底具有較好的緩蝕效果,緩蝕效率隨L-Cys濃度的增大而提高,并隨組裝時(shí)間的延長先小幅下降后提升。利用L-Cys對(duì)C_(18)SH SAMs進(jìn)行兩步法修飾所得的復(fù)合膜較單一分子膜耐蝕性有大幅提高。不同組合方式制備的復(fù)合分子膜的緩蝕效率略有差異,對(duì)此我們提出了相應(yīng)的吸附模型。L-Cys與C_(18)SH混合自組裝膜的膜層內(nèi)分子堆積更致密,腐蝕通道更少,膜層在腐蝕介質(zhì)中更穩(wěn)定,表現(xiàn)出極佳的緩蝕性能。
[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.
【學(xué)位授予單位】：湖南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TG174.46
本文編號(hào)：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.
【學(xué)位授予單位】：湖南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TG174.46
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