3-氨基-1,2,4-三氮唑自组装膜对黄铜的缓蚀作用

3-氨基-1,2,4-三氮唑(ATA)是一种环境友好型金属处理剂, 以其在黄铜表面制备了自组装单分子膜(SAMs), 用电化学方法研究ATA SAMs对黄铜的缓蚀作用及其吸附行为. 结果表明, ATA分子易在黄铜表面形成稳定的ATA SAMs, SAMs抑制了黄铜的阳极氧化过程, 改变了电极表面的双电层结构, 固/液界面双电层电容明显降低, 有良好的缓蚀效果. 研究结果还表明, ATA的吸附行为符合Langmuir吸附等温式, 吸附机理是典型的化学吸附.     

3-氨基-1,2,4-三氮唑和Na_2WO_4复合缓蚀剂对黄铜的缓蚀协同作用

应用交流阻抗和极化曲线测试3-氨基-1,2,4-三氮唑(ATA)和钨酸钠复合缓蚀剂对黄铜在3%NaCl溶液中的缓蚀作用.结果表明,ATA对黄铜有缓蚀作用,并以7.5 mg.L-1ATA的缓蚀效果最好,缓蚀率为87.46%,以7.5 mg.L-1ATA和0.15 mg.L-1Na2WO4配成复合缓蚀剂则对黄铜具有很好缓蚀协同效应,缓蚀效率达91.82%,属阴极型缓蚀剂.     

碱性介质中BIT,BIOHT和BIMMT对铜的缓蚀性能和吸附行为

采用失重法和电化学方法研究了BIT, BIOHT和BIMMT三种席夫碱基四唑类化合物对铜在质量分数为5%的NaHCO3水溶液中的缓蚀性能和吸附行为. 结果表明, 在NaHCO3水溶液中三种化合物对铜均有较好的缓蚀作用, 三种化合物的缓蚀性能大小顺序为BIMMT>BIOHT>BIT. 三种化合物在铜表面上的吸附过程为放热过程, 其在铜表面上的吸附行为服从Langmuir吸附等温式, 属于物理吸附.     

碱性介质中两种Mannich碱对H62黄铜的缓蚀性能和吸附行为

本文采用"一锅法"合成了两种Mannich碱1-(3-氧代丁基)硫脲(OBT)和1-(3-氧代-3-苯丙基)硫脲(OPPT),并采用失重法和电化学研究方法研究了两种Mannich碱对H62黄铜在5%(w)NaHCO3水溶液中的缓蚀性能和吸附行为。结果表明:在5%NaHCO3水溶液中这两种化合物对H62黄铜均有较好的缓蚀效果,缓蚀效率大小顺序为OPPTOBT。并且OBT与OPPT均为阴极型缓蚀剂。两种化合物在铜表面上的吸附过程为放热过程,其在铜表面上的吸附行为服从Langmiur吸附等温式,属于物理吸附。     

非水体系苯并咪唑及衍生物吸附的电化学表面增强拉曼光谱研究

应用电化学现场表面增强拉曼光谱(SERS)以及直接电化学合成技术分别研究了非水体系中苯并咪唑及2-巯基苯并咪唑在铜电极表面的吸附行为及其与三苯基膦(pph3)共存的表面过程.在较负电位区间苯并咪唑主要以分子形式吸附在电极表面.在较正电位区间,电极表面生成类高分子(CuBIM)n膜,具有缓蚀作用,对含有pph3的该体系,Cu+首先与pph3配位形成稳定的阳离子,进入溶液之后与BIM配位生成稳定的配合物,导致不能在表面有效地成膜而破坏了苯并咪唑的缓蚀作用.2-巯基苯并咪唑在Cu表面主要通过自组装单层方式在电极表面吸附,且在实验测试的电位区间内,MBI均是以S端与金属表面作用,其吸附取向随电位正移由倾斜逐渐向接近垂直过渡,并在金属表面形成MBI单分子层膜.pph3的加入不影响MBI在Cu电极表面的成膜行为.电化学现场模拟合成及产物结构组成解析为推断表面反应过程提供了直接证据.     

碱性介质中POTAS和PDTAS对铜的缓蚀作用

合成了两种吡唑啉酮衍生物POTAS 和PDTAS, 并采用失重法和电化学方法研究了这两种吡唑啉酮衍生物对铜在5%(w)NaHCO3水溶液中的缓蚀性能和吸附行为. 结果表明, 在5%NaHCO3水溶液中这两种化合物对铜均有较好的缓蚀作用, 缓蚀效率大小顺序为POTAS>PDTAS. 并且POTAS与PDTAS均为混合型缓蚀剂. 两种化合物在铜表面的吸附均为单层吸附, 属于物理吸附.     

5-苯基-1H-四氮唑对铜片缓蚀性能的研究

通过金相显微镜和接触角测试研究了5-苯基-1H-四氮唑在硫-乙醇体系中对铜的缓蚀性能。结果显示,缓蚀剂可以在铜片表面形成疏水性保护膜,有效抑制了铜片的腐蚀。电化学测试表明,当缓蚀剂浓度为70 mg/L时缓蚀效率达到87%,对铜电极有明显的缓蚀作用。通过量子化学密度泛函理论研究了缓蚀剂分子结构与缓蚀性能的关系,分析了缓蚀剂分子的活性位点。通过分子动力学模拟研究了缓蚀剂分子在Cu的(111)表面的吸附行为。     

表面增强喇曼散射光谱研究金属铜在空气中的氧化及防护

表面增强喇曼散射(SERS)光谱在研究唑类化合物如苯并三氮唑(BTAH),苯并咪唑(BIMH)和2-巯基苯并咪唑(MBIH)在铜表面的行为及缓蚀作用方面已有较多应用。然而这类研究主要在电化学池中进行,存在一定局限性。本文报导利用硝酸蚀刻铜表面,用SERS直接研究铜表面在空气中的氧化以及唑类化合物对此氧化过程的阻碍作用。     

EDA对铜在稀盐酸中的缓蚀效果及硫离子的影响

应用极化曲线塔菲尔区外推法考察了以乙二胺(EDA)作酸性溶液铜缓蚀剂的缓蚀行为以及硫离子对其缓蚀效果的影响.结果表明,在含有EDA的酸性溶液中加入Na2S使铜的腐蚀电位正移,腐蚀速率降低,缓蚀效率提高.溶液中HS-的存在能对EDA的缓蚀作用产生协同效应,这主要是由于HS-在铜表面的强化学吸附,从而更有利于EDA在铜表面形成CuHSEDA吸附保护层,抑制铜的腐蚀.     

2-氨基嘧啶对铜的缓蚀机理

利用动电位极化曲线、线性极化、X射线光电子能谱(XPS)、X射线俄歇能谱(X-AES)和表面增强拉曼散射(SERS)研究2-氨基嘧啶(2-AP)对金属铜的缓蚀作用。结果表明: 在含Cl~-离子的酸性介质中, 2-AP是铜的有效缓蚀剂; 随着介质pH值的增加, 2-AP的缓蚀能力降低。2-AP缓蚀能力随pH值明显变化的原因在于只有在酸性介质中, 质子化了的2-AP分子、Cl~-离子和铜表面原子(或离子)才可能形成保护作用强的多聚配合物膜。     

Corrosion of copper in aerated synthetic sea water solutions and its inhibition by 3-amino-1,2,4-triazole

Corrosion of copper in aerated synthetic sea water (3.5% NaCl) solutions and its inhibition by 3-amino-1,2,4-triazole (ATA) have been studied using electrochemical, gravimetric, and pH measurements, along with Raman spectroscopy. Electrochemical measurements indicated that the presence of ATA and the increase of its concentration suppress the corrosion process on the copper surface. This effect decreases cathodic, anodic, and corrosion (jcorr) currents and corrosion rates (Kcorr), while increasing polarization resistance (Rp), surface coverage (theta), and inhibition efficiency (IE%). Weight loss measurements indicated that the dissolution of copper and the accompanying change of pH decreased to a minimum even after 24 days immersion due to the presence of ATA and the increase of its concentration. Raman investigations revealed that the inhibition of copper corrosion is achieved by strong adsorption of ATA molecules onto the copper surface, preventing it from being corroded easily.     

What determines the inhibition effectiveness of ATA, BTAH, and BTAOH corrosion inhibitors on copper?

Three corrosion inhibitors for copper-3-amino-1,2,4-triazole (ATA), benzotriazole (BTAH), and 1-hydroxybenzotriazole (BTAOH)-were investigated by corrosion experiments and atomistic computer simulations. The trend of corrosion inhibition effectiveness of the three inhibitors on copper in near-neutral chloride solution is determined experimentally as BTAH ? ATA ? BTAOH. A careful analysis of the results of computer simulations based on density functional theory allowed to pinpoint the superior inhibiting action of BTAH and ATA as a result of their ability to form strong N-Cu chemical bonds in deprotonated form. While these bonds are not as strong as the Cl-Cu bonds, the presence of solvent favors the adsorption of inhibitor molecules onto the surface due to stronger solvation of the Cl(-) anions. Moreover, benzotriazole displays the largest affinity among the three inhibitors to form intermolecular aggregates, such as [BTA-Cu](n) polymeric complex. This is another factor contributing to the stability of the protective inhibitor film on the surface, thus making benzotriazole an outstanding corrosion inhibitor for copper. These findings cannot be anticipated on the basis of inhibitors' molecular electronic properties alone, thus emphasizing the importance of a rigorous modeling of the interactions between the components of the corrosion system in corrosion inhibition studies.     

Effects of 3-amino-1,2,4-triazole on the inhibition of copper corrosion in acidic chloride solutions

Effects of 3-amino-1,2,4-triazole (ATA) on the inhibition of copper corrosion in 0.5 M HCl solutions have been studied using gravimetric, electrochemical, and Raman spectroscopy investigations. Weight-loss measurements after varied immersion periods revealed that the dissolution rate of copper decreased to a minimum, while the inhibition efficiency (zeta%) and consequently the degree of surface coverage (theta) increased with the presence of ATA and the increase of its concentration. Potentiodynamic polarization, chronoamperometric, and electrochemical impedance spectroscopy (EIS) measurements after 0, 24, and 48 h immersion of the copper electrode in the test solutions showed that the presence of ATA molecules significantly decreased cathodic, anodic, and corrosion (jcorr) currents and corrosion rates (Rcorr) and greatly increased polarization resistance (Rp), zeta%, and theta; this effect was increased on increasing the ATA content in the solution. Raman spectroscopy confirmed that ATA molecules strongly adsorbed onto the copper surface, blocking its active sites and preventing it from being corroded easily.     

Corrosion inhibition performance of 2-ethyl phenyl-2, 5-dithiohydrazodicarbonamide on Fe (110)/Cu (111) in acidic/alkaline solutions: Synthesis,experimental, theoretical,and molecular dynamic studies

Herein, 2-ethyl phenyl-2,5-dithiohydrazodicarbonamide (2EPDCA) was synthesised and tested as a corrosion inhibitor for mild steel (MS) and copper (Cu) in 1 M HCl and 3.5% NaCl, respectively. Fourier transform infrared spectroscopy (FT-IR) and (NMR) nuclear magnetic resonance (¹H, ¹³C) were used to identify the chemical structure. Both experimental and computational approaches have been conducted to evaluate inhibitor efficiency on both metal systems. The electrochemical results showed that the 2EPDCA inhibition efficiency for MS systems was 95% at 1 × 10^?2 M, while in copper systems it was 97.5% at 1 × 10^?2 M. The Langmuir adsorption isotherm was fitted using adsorption surface coverage data, and for inhibitor in both systems, the kind of adsorption was mixed (physisorption and chemisorption). Through scanning electron microscopy (SEM), EDX, and atomic force microscopy (AFM) tests, we have confirmed the presence of the inhibitor molecules on the metal surface in both systems. Quantum chemistry simulations indicate that the superior corrosion inhibition efficacy of 2EPDCA on copper compared to mild steel surfaces is attributable to the former's greater electron donating propensity on copper. The adsorption of 2EPDCA molecules on Fe (110) and Cu (111) surfaces was further verified by molecular dynamic simulations, with the former having a greater adsorption energy. The results indicate that the corrosion inhibitor was effective even in harsh conditions, and it can be thought of as a novel corrosion inhibitor for mild steel and copper that provides good protection.     

Employing electrochemical frequency modulation for studying corrosion and corrosion inhibition of copper in sodium chloride solutions

The inhibition effect of 2-carboxymethylthio-4-(p-methoxyphenyl)-6-oxo-1,6-dihy-dropyrimidine-5-carbonitrile (CPD) towards the corrosion of copper was studied in aerated stagnant 3.5% NaCl at 25 °C using ac techniques include electrochemical frequency modulation and electrochemical impedance spectroscopy as well as potentiodynamic polarization measurements. Corrosion rates determined using electrochemical frequency modulation (EFM) which measures the non-linear behaviour of a corroding system are compared with corrosion rates obtained from traditional electrochemical techniques and show good agreement. Data obtained from EIS were analyzed to model the corrosion inhibition process through equivalent circuit. Polarization measurements showed that CPD acts as mixed-type inhibitor. The inhibition efficiency increases with an increase in the concentration of CPD. The adsorption of the inhibitor on the copper surface in the sodium chloride solution was found to obey Langmuir’s adsorption isotherm. A mixed inhibition mechanism is proposed for the inhibitive effects of CPD as revealed by potentiodynamic polarization technique.     

Inhibition of copper corrosion by bipyrazole compound in aerated 3% NaCl

The corrosion behaviour of copper in aerated 3% NaCl solution was investigated by rotating electrode at various rates. The reduction of O₂ obeys the Levich equation. The inhibition of the copper corrosion in aerated 3% NaCl solution was studied by using potentiodynamic polarisation and linear polarisation resistance (LRP) in the presence of different concentrations of a bipyrazolic compound named N,N-bis (3-carbomethoxy-5-methylpyrazol-1-ylmethyl) cyclohexylamine (BiPyA). The presence of this compound in the solution decreases the corrosion current density and increases the linear resistance polarisation. The inhibition efficiencies obtained from cathodic Tafel plots and LRP methods are in good agreement. BiPyA compound presents an efficient inhibitor of copper corrosion, acts as a mixed-type inhibitor and adsorbs on the copper surface according to the Langmuir isotherm model.     

复方钨酸盐对铜缓蚀协同作用的光电化学和SERS 研究

主要采用光电化学方法和表面增强拉曼光谱技术对具有环境友好性的钨酸盐与BTA复配使用对铜的缓蚀协同效应和作用机理进行了研究。实验表明Na2WO4对铜的缓蚀作用机理与BTA不同,在电位正向扫描过程中,光电流并不发生转型,其大小变化也不大;但在电位负向扫描过程中产生的阴极光电流峰值明显增大,缓蚀剂浓度越大,光电流越大,缓蚀效果越好,而Na2WO4与BTA复配使用时具有较好的协同效应,光电化学和SERS结果都说明其协同机理为两者都能对铜的缓蚀产生作用,前暑能促使电极表面产生的铜的氧化物增多;后者能与铜(Ⅰ)生成聚合物膜。     

铜电极表面硅烷膜的自组装及其性能研究

应用自组装技术在铜电极表面上制备3巯基丙基三甲氧基硅烷自组装膜.红外光谱研究该自组装膜结构,电化学方法考察3-巯基丙基三甲氧基硅烷膜在5%NaCl溶液中对铜电极的缓蚀性能.结果表明,于不同浓度的3-巯基丙基三甲氧基硅烷乙醇溶液中自组装的硅烷膜表现出较好的抗腐蚀性.     

MMI作为铜的盐酸酸洗缓蚀剂作用机理的研究

用失重法研究了N-甲基-2-巯基咪唑（MMI）在5％盐酸中对铜的酸洗缓蚀性能.探讨了温度和MMI浓度对缓蚀效果的影响，从中得出了MMI在铜表面的吸附等温式，计算了吸附热及MMI的加入对铜在盐酸中腐蚀反应活化能的影响，进而探讨了MMI对铜缓蚀作用的机理.结果表明， 30 ℃下，在5％盐酸中，当MMI的浓度在3 mmol•L－1和8 mmol•L－1之间时,缓蚀率随MMI浓度的增加而迅速增加，当浓度达到8 mmol•L－1时，缓蚀率趋于定值，而当浓度小于3 mmol•L－1时， MMI的加入会加速铜的腐蚀；吸附在铜表面的MMI分子间的作用力整体表现为引力； MMI在铜表面的吸附是吸热反应； MMI的加入降低了铜的腐蚀反应活化能.