BTA系列Cu缓蚀剂的电化学行为

采用交流阻抗法和恒电位阶跃法研究了在硼砂缓冲溶 液（pH9.2）中BTA及其系列衍生物CBTME,CBTBE对Cu电极的缓蚀行为.结果表明：BTA对Cu 的缓蚀作用是由于在Cu表面上生成了Cu/Cu2O/Cu(I)BTA膜,阻滞了Cu的腐蚀,而且缓蚀剂 的浓度越高,生成的Cu/Cu2O/Cu(I)BTA膜越致密,抑制作用越强.含CBTME缓蚀剂的溶液 中,缓蚀效果随缓蚀剂浓度的升高而增强,但同浓度比较时,BTA的缓蚀效果优于CBTME.当 溶液中含有较低浓度CBTBE时,缓蚀剂促进Cu的腐蚀;而当溶液中含有较高浓度CBTBE时,缓 蚀剂才抑制Cu的腐蚀.一定比例的BTA和CBTME复配后对Cu的缓蚀作用有协同效应.以5 mg/L 为缓蚀剂总量,其最佳复配方案为2 mg/L BTA+3 mg/L CBTME.恒电位阶跃法测得的结果与 交流阻抗方法测得的结果相符.     

3%NaCl溶液中铜的表面膜及BTA膜的光电化学研究

３％ＮａＣｌ溶液中铜的表面膜及ＢＴＡ膜的光电化学研究任聚杰，杨迈之，童汝亭，蔡生民（河北医学院石家庄０５００１７）（北京大学北京１００８７１）（河北师范大学石家庄０５００１６）１引言人们已经注意到Ｃｌ－对Ｃｕ有腐蚀作用［１，２］，关于ＢＴＡ对Ｃｕ的缓...     

3%NaCl溶液中咪唑和苯并三唑对Cu缓蚀协同作用的研究

采用失重法考察了3%NaCl溶液中咪唑和苯并三唑对Cu 的缓蚀作用,结果表明100 mg/L的咪唑对Cu的缓蚀率仅为477%,100 mg/L的苯并三唑对Cu 的缓蚀效率为732%,当70 mg/L的咪唑和30 mg/L的苯并三唑复配使用后,其缓蚀效率提高 到943%,电化学极化曲线研究表明苯并三唑对Cu电极的阳极过程有抑制作用,咪唑对Cu电 极的阴极过程有抑制作用,咪唑和苯并三唑的复配使用显著增加了对Cu电极阴极和阳极电化 学过程的抑制作用.     

Adsorbed corrosion inhibitors studied by electron spectroscopy: Benzotriazole on copper and copper alloys

Surface films formed by adsorption of benzotriazole (BTA), on copper and copper alloys have been studied by X-ray photo-electron spectroscopy (XPS). It is found that on both copper and copper-nickel alloys, benzotriazole forms a Cu(I)BTA surface complex. For the copper-nickel alloys the time taken to form the Cu(I)BTA film is dependent on the alloy composition. The Cu(I)BTA films were found to oxidize rapidly to a Cu(II) species on removal from the liquid phase. Surface films formed by BTA on 70 Cu : 30 Zn alloy were found to contain both copper and zinc, the copper again being in the Cu(I) state.A study of the adsorption of BTA on cathodically reduced copper surfaces strongly supports previous suggestions that the presence of Cu₃O facilitates formation of the surface film.     

Cu-Ni合金BTA复配体系钝化处理工艺研究

采用苯并三氮唑(BTA)复配钝化体系对B10 Cu-Ni合金进行钝化处理,以提高其在含硫化物环境介质中的耐腐蚀性能,并研究工艺参数对钝化膜耐蚀性的影响规律.利用动电位极化曲线和电化学阻抗谱研究钝化膜的耐腐蚀性能,采用X射线光电子能谱分析钝化膜的化学成分.实验结果表明,在BTA与磺基水杨酸组成的复配体系中形成的钝化膜比BTA单一体系中形成的钝化膜具有更高的耐蚀性,这是磺基水杨酸与基体合金反应形成的络合物膜与Cu(I)BTA膜协同作用的结果;钝化处理的时间和温度是影响钝化膜耐蚀性的重要工艺参数,延长钝化时间和提高钝化温度均可以提高钝化膜的耐蚀性,60℃高温条件下5 min的钝化处理即能够达到常温条件下3 h的钝化处理效果.     

苯并三唑对碳钢/铜合金电偶腐蚀行为的影响

目的 研究NaCl溶液中苯并三唑(BTA)对碳钢/铜合金电偶腐蚀行为的影响.方法 使用丝束电极(WBE)技术和电化学阻抗谱(EIS)技术研究在未添加和添加BTA的NaCl溶液中,丝束电极表面的电位分布、电流密度分布和电化学阻抗谱演化,同时对比分析碳钢区域与铜合金区域的阻抗谱特征.结果 在未添加BTA的条件下浸泡72 h...     

苯并三氮唑与4—羟基苯并三氮唑在氯化钠溶液中对铜的缓蚀作用

用表面增强拉曼光谱技术（SERS）对在3％NaCl溶液中苯并三氮唑（BTA）及其衍生物4－羟基苯并三氮唑（4CBTA）对铜的缓蚀作用机理进行了研究,发现4CBTA对铜的缓蚀作用机理与BTA相似,在较正电位下两者都是通过三唑环与铜形成配合物覆盖在铜表面随着电位负移,铜电极表面吸附的分子形式的BTA或4CBAT数量增多;4CBT中的－COOH基团只是起到空间位阻的作用,没有参与电极表面的吸附,两者复配使用时以BTA吸附为主,其缓蚀机理没有发生改变。也没有产生协同效应。     

黄铜表面多层化学转化膜特性研究

黄铜经苯并三氮唑(BTA)和络合钝化剂PVA溶液钝化处理后,表面耐蚀性明显提高,椭圆偏振法和X射线光电子能谱法(XPS)研究表明,PVA能在Cu(I)BAT薄膜上继续外延生长成膜,BTA—PVA混合液钝化处理效果与先用BTA、后用PVA溶液钝化处理效果基本相同、钝化处理后的化学转化膜大体上为三层结构,即Cu_2O/Cu(I)BTA/PVA膜     

苯并三唑和咪唑分子内缓蚀协同作用的研究

通过Ｍａｎｎｉｃｈ反应把苯并三唑和咪唑分子用亚甲基链连接起来,合成１－「１’－咪唑）－甲基」苯并三唑化合物,采用静态挂片法,电化学极化曲线法和电化学阻抗法研究了它对３％ＮａＣｌ溶溶中铜的缓蚀作用,讨论了分内苯并三唑单元和唑唑单元的协同缓蚀作用。     

复配BTA与TTA钝化纯铜工艺研究

目的为了提高纯铜表面的耐腐蚀性。方法通过苯并三氮唑(BTA)与甲基苯并三氮唑(TTA)复配,对纯铜进行钝化,并分析钝化温度、时间及pH值对纯铜钝化效果的影响。分别运用电化学法、硝酸点滴实验、中性盐雾实验、SEM等手段对不同钝化液钝化膜的微观结构与耐蚀性能进行研究,并与铬酸盐钝化结果进行对比。结果将4 g/L BTA、4 g/L TTA复配,辅以氧化剂20 m L/L H_2O_2,对纯铜以pH值为4、钝化时间3 min、钝化温度40℃、自然风干老化1 d的钝化工艺处理后,可以生成明显的钝化膜。其表面致密,耐蚀性较好,在盐雾试验中腐蚀缓慢,其平均腐蚀速率为0.76 mg/d,自腐蚀电流密度仅为1.5660μA/cm2,缓蚀率达到81.9%,接近铬酸盐钝化的抗腐蚀效果。结论在适宜的钝化工艺下,经过BTA与TTA复配钝化后,可以在基体表面生成Cu/Cu_2O/Cu(I)BTA聚合物保护膜,同时TTA的非极性甲基形成的单分子层膜的疏水性更好,两者共同作用,形成较为致密的钝化膜覆盖在铜基体表面,明显提高纯铜表面耐蚀性。     

铜表面BTA薄膜在强酸中耐蚀性的电化学阻抗研究

用电化学阻抗法研究铜在强酸中添加BTA(苯并三唑)及铜表面预覆BTA薄膜后在强酸中的耐蚀行为和机理。研究表明:在强酸溶液中,BTA与二价铜离子形成不同配位数的Cu—BTA配合物,在硫酸中抑制阳极反应,在盐酸中抑制阴极反应。在铜表面预覆BTA薄膜,对铜有更好的防蚀保护性能。     

Kinetics of corrosion inhibition of benzotriazole to copper in 3.5% NaCl

The kinetics of interaction of benzotriazole (BTAH) with the surface of copper were studied using an electrochemical quartz crystal microbalance (EQMB) and electrochemical impedance spectroscopy (EIS). Upon injecting BTAH into the electrolyte, three regions appear in the time response of the microbalance. Region I (at short time scale of few minutes) exhibits rapid linear growth of mass with time. This is attributed to the formation of a Cu(I)BTA film that is several hundred layers thick. Region II reveals adsorption of BTAH at a slower rate, on the inner Cu(I)BTA complex. Region III is a plateau indicating that the BTAH film attains an equilibrium thickness, which increases with the concentration of BTAH. The polarization resistance of the interface changes with time in a similar fashion while the double layer capacitance decreases. The results suggest that the thickness of the physically adsorbed film of BTAH increases with time and BTAH concentration while the thickness of the inner Cu(I)BTA remains constant. Two semicircles were obtained in the impedance spectra corresponding to the complex Cu(I)BTA and the physically adsorbed BTAH.     

Impedance and XPS study of benzotriazole films formed on copper, copper-zinc alloys and zinc in chloride solution

The formation of protective layers on copper, zinc and copper-zinc (Cu-10Zn and Cu-40Zn) alloys at open circuit potential in aerated, near neutral 0.5 M NaCl solution containing benzotriazole was studied using electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS). Benzotriazole (BTAH), generally known as an inhibitor of copper corrosion, also proved to be an efficient inhibitor for copper-zinc alloys and zinc metal. The surface layers formed on alloys in BTAH-inhibited solution comprised both polymer and oxide components, namely Cu(I)BTA and Zn(II)BTA polymers and Cu₂O and ZnO oxides, as proved by the in-depth profiling of the layers formed. A tentative structural model describing the improved corrosion resistance of Cu, Cu-xZn alloys and Zn in BTAH containing chloride solution is proposed.     

A novel process for copper protection in the simulated industrial cooling water based on click synthesis and self‐assembling method

The triazole inhibitor of 1‐(p‐tolylthio)‐1H‐1,2,3‐triazole‐4‐carboxylic acid (TTC) was synthesized via the Cu(I)‐catalyzed azide‐alkyne 1,3‐dipolar cycloaddition reaction. The self‐assembling method was performed to fabricate the self‐assembled film of TTC on the copper surface. The electrochemical measurement results indicate that the TTC film can efficiently protect the copper from corrosion in high concentrated industrial cooling water. The protection efficiency of TTC film for copper is 92.2%. Surface characterizations imply that the copper with TTC film after corrosion is covered with multiple protective layers. It probably contains Cu(I) and Cu(II) complexes mixed with nitrogenous compound, Cl^? and SO₄^2?. The result of quantum chemical calculation shows that the superior performance of TTC film is related to the adsorption of TTC molecules on copper surface horizontally. This kind of adsorption is mainly achieved via the adsorption centers of triazole ring and O atoms in TTC molecule.     

Corrosion inhibition of copper–phosphorus brazing alloys in tetra‐n‐butylammonium bromide aerated aqueous solution by benzotriazole

The corrosion inhibition behavior of benzotriazole (BTA) on a brazing alloy, CuP in the non‐welded and welded conditions in 17 wt% (0.534 mol/L) tetra‐n‐butylammonium bromide (TBAB) aerated aqueous solution was investigated by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy/energy dispersive X‐ray spectroscopy techniques. The experimental results showed that BTA could protect effectively copper alloys in aqueous TBAB solution. The inhibition efficiency of BTA increased with increasing inhibitor concentration from 0.1 to 6 g/L, attaining efficiencies of up to 96% calculated according to different methodologies. Corrosion current densities were lower after the melting process. Galvanic studies showed that copper behaved as the anode when coupled to its alloys. The addition of BTA caused an increase in charge transfer resistance and a decrease in the capacitance of the double layer. Adsorption of BTA in 17 wt% TBAB solution on the copper alloys' surface was found to obey the Langmuir adsorption isotherm.     

The synergistic effect of Na3PO4 and benzotriazole on the inhibition of copper corrosion in tetra‐n‐butylammonium bromide aerated aqueous solution

The effect of Na₃PO₄ and the mixture of benzotriazole (BTA) and Na₃PO₄ (SP) on the corrosion of copper in 17 wt% (0.534 mol/L) tetra‐n‐butylammonium bromide (TBAB) aerated aqueous solution has been investigated by means of weight‐loss test, potentiodynamic polarization test, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy/energy dispersive X‐ray techniques. The experimental results showed that a dosage of Na₃PO₄ stimulated the copper corrosion, and the corrosion rate increased with increasing Na₃PO₄ concentration, whereas the mixture of BTA and Na₃PO₄ could protect copper in aqueous TBAB solution. The inhibition action of the mixture of BTA and Na₃PO₄ on the corrosion of copper is mainly due to the inhibition of the anodic process of corrosion. The inhibition efficiency of a mixture consisting of 2 g/L BTA and 1 g/L Na₃PO₄ was about 96%. The mixture of BTA and Na₃PO₄ inhibits the corrosion of copper better than BTA by itself, indicating that Na₃PO₄ has a synergistic role with BTA on the corrosion inhibition of copper in TBAB aqueous solution.     

Corrosion inhibition of copper by 2,5-dimercapto-1,3,4-thiadiazole monolayer in acidic solution

2,5-Dimercapto-1,3,4-thiadiazole (DMTD) monolayer was self-assembled on the fresh copper surface to form protective monolayer against copper corrosion in acidic solution. Its corrosion inhibition was investigated in 0.5 M HCl by cyclic voltammetry, potentiodynamic polarization and electrochemical impedance spectroscopy methods. The results revealed that the DMTD monolayer inhibited the copper corrosion effectively with the optimum self-assembly time of 10 h and the optimum self-assembly concentration of 7.5 mM. Surface observation was performed using scanning electron microscope, contact angle goniometer and Fourier transform infrared spectrometer. The molecular simulation has been used to simulate the adsorption model of DMTD molecule on Cu(1 1 1) surface.     

Corrosion inhibition of copper in tetra‐n‐butylammonium bromide aqueous solution by benzotriazole

The corrosion inhibition behavior of benzotriazole (BTA) on copper in 17 wt% tetra‐n‐butylammonium bromide (TBAB) aerated aqueous solution was investigated by weight‐loss tests, potentiodynamic polarization, electrochemical impedance spectroscopy, and scanning electron microscopy/energy dispersive X‐ray spectroscopy. BTA is a good inhibitor in 17 wt% TBAB solution. The inhibition efficiency of BTA increases with increasing inhibitor concentration, attaining efficiencies of up to 90% calculated according to different methodologies. Adsorption of BTA in 17 wt% TBAB solution on the copper surface was found to obey the Langmuir adsorption isotherm.     

磷酸基钝化电解液电化学射流加工铜的材料去除机理分析

目的 提高电化学射流(Jet-ECM)加工纯铜工件的加工稳定性和表面质量,并分析材料去除机理.方法 采用基于磷酸基的酸性钝化电解液.该酸性钝化电解液采用磷酸为黏膜生成剂,乙醇为润湿剂,苯并三氮唑(BTA)为腐蚀抑制剂,醋酸铵和乳酸为表面氧化物去除剂.分别通过极化曲线,阻抗测试揭示磷酸溶液中黏膜层的生成机理,并通过循环伏...     

1 : 2 : 4-triazole as a corrosion inhibitor for copper

The solution chemistry of 1 : 2 : 4-triazole (TRZ) is investigated in the range of solution concentrations in which the compound acts as a corrosion inhibitor for copper. Parallel photo-electron spectroscopic studies show that although a surface layer of Cu(I) complex is formed at low TRZ concentrations, this is ineffective as an inhibitor until at a critical concentration a Cu(II) complex appears which provides effective protection. It is suggested that the precipitation of Cu(II) hydroxychloride is which the TRZ is attached provides the protective layer. Comparison is made between triazole and benztriazole as corrosion inhibitors for copper.