原子力显微镜研究苯并三氮唑对铜的缓蚀作用

铜以及铜合金由于其优良的抗腐蚀性能,广泛用在冷却水系统中,苯并三氮唑(BTA)常常作为铜的缓蚀剂。将传统电化学方法和原子力显微镜(AFM)测试技术相结合,对人造海水中BTA作用于铜电极的缓蚀行为进行了研究。结果表明,BTA能够有效减缓铜在海水中的腐蚀,且随着缓蚀剂浓度的增加,缓蚀效果越明显,100 mg/L的BTA就能够高效的保护铜。电化学结果表明,BTA能够在铜的表面形成致密的保护膜[CuBTA]n;AFM测试表明,随着时间的进行,保护膜越来越致密,保护性能也越好。     

苯并三氮唑及其衍生物对铜的协同缓蚀效应

以苯并三氮唑(BTA)和溴代正丁烷为原料,采用一步法合成了N-丁基苯并三氮唑(N-BBTA),研究了BTA、N-BBTA以及N-BBTA与BTA的复配体系对铜在3％(质量分数)NaC1溶液中的缓蚀行为.结果表明,单一N-BBTA和BTA对铜均具有一定的缓蚀能力.当N-BBTA、BTA浓度为10 mmol/L时,缓蚀率分...     

The effect of benzotriazole on mass transfer in the corrosion of a copper rotating disk electrode

The effect of benzotriazole, BTA, on mass transfer in dissolution-corrosion of the copper rotating disk electrode in 0.02 M Fe(III)–0.5 M H₂SO₄ has been studied by means of atomic absorption spectrometry. The mass transfer coefficient, K, was determined from the slope of ln(C ₀/C)_Fe(III) vs. time plots. In the absence of BTA the corrosion process can be described by the correlation Sh = KR/D = 4.47Re ^0.5. The difference in values between Sh and Sh _Levich, and the change in slope in the Arrenhius plot points to mixed control for the cathodic process Fe³⁺ + 1e^– Fe ²⁺ and charge transfer control for the anodic process, Cu Cu²⁺ + 2e. The average activation energies were 7.7 kJ mol^–1 and 19.5 kJ mol^–1 at (500–1500) and (2000–3000) rpm, respectively. At low concentration of BTA the inhibiting action of BTA increases with concentration and with rotation speed. For [BTA] 5 × 10^–3 M, the K value, 10^–4 cm s^–1, remains constant and is independent of rotation rate. The morphology of the copper rotating disk after corrosion in the absence and presence of BTA was examined using scanning electron microscopy (SEM).     

An electrochemical and Raman spectroscopic investigation of synergetic effects in the corrosion inhibition of copper

The synergetic inhibition of copper corrosion by benzotriazole (BTA) and benzylamine (BZA) in chloride and cyanide media is assessed by voltammetric and ac impedance measurements. BZA enhances the performance of the strong inhibitor BTA by accelerating the growth of a protective surface layer; used alone, BZA is ineffective as an inhibitor. The competitive adsorption of aggressive anions and inhibitors is studied by surface enhanced Raman scattering (SERS). The dramatic increase in corrosion caused by low concentrations of cyanide ions is shown to be due to the displacement of BTA from the copper electrode surface; comparisons are made with the behaviour of mercaptobenzoxazole (MBO).     

Experimental and atomistic simulation studies of corrosion inhibition of copper by a new benzotriazole derivative in acid medium

The efficiency of N-(2-thiazolyl)-1H-benzotriazole-1-carbothioamide (TBC) as a non-toxic corrosion inhibitor for copper in 0.5 M HCl has been tested by weight loss and electrochemical techniques. Electrochemical techniques show that TBC is a mixed-type inhibitor and its inhibition mechanism on copper surface is adsorption assisted by H-bond formation. Impedance measurements show a wide peak presumably given by more than one time constant in the presence of TBC. Also, impedance results show that the values of CPEs (constant phase elements) tend to decrease and both polarization resistance and inhibition efficiency tend to increase with increasing of TBC concentration due to an increase in the electric double layer. Monte Carlo simulations incorporating molecular mechanics and molecular dynamics show that the TBC adsorb on the copper surface firmly through the thiazolyl and carbothioamide groups, the adsorption energy as well as hydrogen bond length have been calculated for both TBC and benzotriazole (BTA) for comparison. Quantum chemical calculations reveal that TBC has higher HOMO, lower LUMO, lower energy gap and lower dipole moment (μ) than BTA, which proves that TBC is better copper corrosion inhibitor compared with BTA in 0.5 M HCl.     

氧化型杀生剂对苯并三氮唑缓蚀性能影响的研究

对苯并三氮唑在氧化型杀生剂作用下的氧化反应机理进行了分析,苯并三氮唑被氯氧化后其缓蚀效果会下降,提出了含氧化型杀生剂循环水中提高苯并三氮唑缓蚀效果的措施,在工业应用中取得了良好的效果.     

On the corrosion inhibition and adsorption behaviour of some benzotriazole derivatives during copper corrosion in nitric acid solutions: a combined experimental and theoretical study

Copper corrosion inhibition in 1 M HNO₃ solution by some benzotriazole derivatives, namely N-(2-thiazolyl)-1H-benzotriazole-1-carbothioamide (TBC), N-(furan-2-ylmethyl)-1H-benzotriazole-1-carbothioamide (FBC) and N-benzyl-1H-benzotriazole-1-carbothioamide (BBC), was investigated by ac impedance, dc polarization and weight loss techniques. A significant decrease in the corrosion rate of copper was observed in presence of the investigated compounds. The corrosion rate was found to depend on the concentration and type of the inhibitor. The degree of surface coverage of the adsorbed inhibitor was determined by weight loss technique, and it was found that the results obeyed Langmuir adsorption isotherm. Tafel polarization data indicated that the three selected inhibitors were of mixed type. The reactivities of the compounds under investigation were analyzed through Fukui indices, derived from density functional theory (DFT), to explain their inhibition performance.     

A review of the effects of benzotriazole on the corrosion of copper and copper alloys in clean and polluted environments

A continuing challenge in materials design is the achievement of high operational efficiency through improvements in performance criterion, particularly its service life-time characteristics. Benzotriazole (BTAH) has now been in use for many years for the protection of copper and copper alloys against various forms of corrosion. In this review, the chemistry of BTAH and theories regarding its mode of action are summarized. Also, a survey of the reported work in both clean and polluted environments is documented. More interestingly, the adverse effect of BTAH on the corrosion of Cu and Cu alloys in sulfide polluted environments is introduced.     

Pitting corrosion of polycrystalline annealed copper in alkaline sodium perchlorate solutions containing benzotriazole

The pitting corrosion of copper in alkaline solutions in the presence of benzotriazole (BTA) was investigated. The presence of BTA shifts the breakdown (E _b) and the repassivating (E _p) potentials positively with respect to the blanks. However, the shift ofE _p becomes smaller than that ofE _b, particularly at pH9 and 11. Pitting corrosion involves the formation of crystallographic pits. The kinetics of the process fits a nucleation and growth mechanism involving instantaneous nucleation and 3D growth under charge transfer control. The spatial distribution of pits indicates that there is no marked influence of a pit on the nucleation and growth of other pits.     

Investigation of copper corrosion inhibition by STM and EQCM techniques

The mechanism of copper corrosion and its inhibition were studied using electrochemical techniques, in situ scanning tunneling microscopy (STM) and electrochemical quartz crystal microbalance (EQCM) methods. The morphological changes of Cu (111) were followed in 0.1 M Na₂SO₄ solution at pH 2.95. The adsorption of 5-mercapto-1-phenyl-tetrazole (5-McPhTT) at different concentrations was studied. The anodic dissolution of copper in 0.1 M Na₂SO₄ was clearly modified and hindered by the addition of 5-McPhTT. The anodic current density was reduced sharply due to the adsorption of the inhibitor on the metal surface thus providing protection. EQCM data revealed that the addition of the inhibitor to the aggressive solution did not cause a continuous increase in the electrode mass. This fact indicates that the inhibitor effect in hindering copper corrosion was due to the adsorption of a monolayer or even a submonolayer.     

Effect of benzotriazole (BTA) addition on Polypyrrole film formation on copper and its corrosion protection

Benzotriazole (BTA) was added in a conducting Polypyrrole (PPy) film prepared on copper in oxalic acid aqueous solution containing pyrrole monomer to improve corrosion protection by the PPy film and reduce copper corrosion. When BTA was added in the preparation solution, the copper surface was covered by a BTA–Cu complex layer before the anodic polymerization of PPy was started. On the copper surface with the BTA layer, the initial dissolution of copper was inhibited and the PPy polymerization-deposition was started immediately after the anodic current was imposed. The PPy film thus formed was doped with oxalic ions and ionized BTA and was homogeneous in thickness and strongly adhesive. The PPy film containing BTA protected the copper from corrosion in 3.5 wt.% NaCl solution. In 400 h of immersion, copper dissolution was inhibited with 80% protection efficiency relative to that of bare copper.     

Synergism in copper corrosion inhibition by sodium dodecylbenzenesulphonate and 2-mercaptobenzoimidazole

The inhibition effects of sodium dodecylbenzenesulphonate (SDBS) and 2-mercaptobenzoimidazole (2-MBI) on the corrosion of copper in sulphuric acid solution have been studied using electrochemical impedance spectroscopy (EIS) and Tafel polarisation measurements. For 2-MBI, a monotonic increase in inhibition efficiency is observed as a function of concentration. Upon mixing 2-MBI and SDBS, concentration regions showing synergistic inhibition behaviour are identified and it is concluded that electrostatic interactions between adsorbate ions are likely responsible for both phenomena. Different adsorption isotherms were tested for relevance in describing the adsorption behaviour of both 2-MBI and SDBS. 2-MBI obeys the Langmuir isotherm and SDBS adsorption is described successfully by the Temkin isotherm.     

规整有机分子自聚集体对铜的高效缓蚀的研究

通过多步法合成了离子型含双苯并三氮唑环的目标分子,4,4’-{苯-1,3-二基二[(1E)-3-羰基丙-1-烯-1,3-二基]}二[2-(2H-苯并三唑-2-基)苯醇酸]二钾。在室温条件下,目标分子在3.5%(质量) NaCl/DMSO(二甲基亚枫)混合溶液(体积比:40/60)中能够发生分子自组装产生纳-微米级的自聚集体。通过傅里叶变换红外光谱(FT-IR)、拉曼光谱和X射线光电子能谱(XPS)的表征,证实了所形成的目标分子自聚集体能够对铜表面产生强烈的化学吸附作用,在铜表面形成自组装膜。利用电化学方法测定了目标分子自聚集体吸附在铜表面形成自组装膜后,在3.5%(质量) NaCl溶液中的缓蚀性能。结果表明目标分子自聚集体在NaCl溶液中能高效地抑制铜腐蚀。     

Study on highly efficient corrosion inhibition of copper by regular self-aggregates of organic molecule

This study presents synthesis of target ionic bistriazole rings-based molecule, 4,4'-{benzene-1,3-diylbis[(1E)-3-oxoprop-1-ene-1,3-diyl]}bis[2-(2H-benzotriazol-2-yl)phenolate] dipotassium (BDBD), through multi-step preparation route. At room temperature, the target molecule can self-assemble to produce nano-micron self-aggregates in a 3.5%(mass) NaCl / DMSO (dimethyl maple) mixed solution (volume ratio, 40/60). It is shown that the predominantly strong chemical adsorption of the formed molecular self-aggregates on the studied copper specimen leads to the yield of self-assembly film on copper surface, which is characterized by FT-IR, Raman and XPS spectroscopy. The corrosion inhibition performance of the stable self-aggregates adsorbed-copper specimens in 3.5%(mass) brine solution based on electrochemical method is surveyed. The results show that the target molecular self-aggregates can effectively inhibit copper corrosion in NaCl solution.     

Electrochemistry and surface analysis of the effect of benzotriazole on the cut edge corrosion of galvanized steel

The effect of benzotriazole (BTAH) in high concentration on the cut edge corrosion of galvanized steel in sodium chloride solution was studied, using electrochemical polarization, EIS, SVET and XPS. It was observed that there is the formation of a BTAH surface film on both steel and zinc, which polarizes anodically both metals, greatly reducing their electrochemical activity and changing the rate control from diffusion at the cathode to mixed control. The protective film undergoes numerous events of local activation and repassivation. The XPS data revealed that the BTAH becomes differently bound to zinc depending on the metal being under self-corrosion or coupled to steel. Although the BTAH reduces the electrochemical activity of both materials, there is significant reduction of the cathodic protection effect of zinc.     

Synergistic effect of 2-mercapto benzimidazole and KI on copper corrosion inhibition in aerated sulfuric acid solution

2-Mercapto benzimidazole (MBI) was used as a copper corrosion inhibitor in aerated 0.5 mol L^–1 H₂SO₄ solutions. The inhibition efficiency (IE) increased with increasing MBI concentration to 74.2% at the 1 mM level. A synergistic effect existed when MBI and iodide ions were used together to prevent copper corrosion in sulfuric acid. It was found that IE reached 95.3% in 0.5 mol L^–1 H₂SO₄ solutions containing 0.75 mmol L^–1 MBI and 0.25 mmol L^–1 KI. X-ray photoelectron spectroscopy (XPS) analysis of the copper samples showed that a (Cu⁺MBI) complex film formed on the surface to inhibit the copper corrosion and the iodide ions did not participate in the formation of the inhibitor film. The synergistic effect was attributed to the adsorption of iodide anions on the copper surface, which then facilitated the adsorption of protonated MBI and the formation of an inhibitive film.     

铜材质酸洗复合缓蚀剂Lan-826和苯并三氮唑的最佳配比

详细考察了在对铜及铜合金进行酸洗过程中,单独加入Lan-826、苯并三氮唑以及按不同配比混合加入时腐蚀率的变化情况,确定了混合加入缓蚀剂的最佳配比。     

BTA与表面活性剂O-20复配对铜CMP缓蚀行为的研究

通过电化学和化学机械抛光实验,研究了铜互连CMP中低浓度缓蚀剂BTA和非离子表面活性剂O-20复配对Cu电化学腐蚀及去除速率的影响,同时利用扫描电子显微镜(SEM)和原子力显微镜(AFM)表征了Cu表面形貌。电化学实验结果表明,在双氧水、甘氨酸体系下,0.5 mmol/L BTA与0.5 mmol/L O-20复配后,Cu表面腐蚀减少,其缓蚀效率动态条件下为59.58%,静态条件下为85.36%,相当于1mmol/L BTA的缓蚀效率。CMP实验结果表明,BTA与O-20复配后,Cu的去除速率为113 nm/min,表面微粗糙度降低,可达0.953 nm。使用低浓度BTA与O-20复配能抑制Cu表面腐蚀,降低Cu表面抛光后的微粗糙度,并且有利于CMP后清洗。     

用扫描隧道显微镜研究铜表面苯并三氮唑吸附膜的结构形态

It is observed by scanning tunneling microscopy (STM) that the adsorbed Benzotriazole (BTA) on copper is long in shape and has an irregular rectangle.The growth of BTA on copper is in the from of polymeric chain and mainly in one dimension rather than two dimensions.The copper surface covered by BTA becomes flatter,smoother and the roughness was smaller than that of bare copper,so the corrosion is largely decreased.However,many grooves can be seen between BTA polymeric chains in which corrosion may exist to a degrees.     

钼膦系药剂缓蚀协同效应的研究

通过旋转挂片失重法研究了钼酸钠,羟基乙叉二膦酸和锌盐组成三元体系在水介质中对Ａ３钢的缓蚀作用,它们之间有着显著的协同效应,实验规律性的研究对开发新的钼膦系药剂具有实际的指导意义。