Copper(II) 8-hydroxyquinolinate 3D network film with corrosion inhibitor embedded for self-healing corrosion protection

This work presents a self-healing protective coating for copper. The complex coating is composed of copper(II) 8-hydroxyquinolinate (Cu(8HQ)₂) 3D network film storing corrosion inhibitor as base layer and epoxy as top layer covering on the base layer. The results of EIS and polarization curves reveal the self-healing effect of Cu(8HQ)₂ 3D network film with corrosion inhibitor embedded. After being scratched with a knife-edge, the complex coating rapidly releases inhibitor embedded in 3D network structure to suppress the corrosion process. The scratch on the coating is covered with inhibitor adsorption film and the anodic activity is restrained.     

Role of alloyed copper on corrosion resistance of austenitic stainless steel in H2S–Cl− environment

Corrosion test, surface analysis and thermodynamic calculation were carried out in the H₂S–Cl⁻ environments to clarify the role of alloyed Cu on the corrosion resistance of austenitic alloys. The alloyed Cu improved pitting corrosion resistance in the H₂S–Cl⁻ environment. The surface film of Cu-containing alloy indicated double layer consists of copper sulfide and chromium oxide, and the copper sulfide was able to exist stably compared to iron sulfide and nickel sulfide. It is concluded that the copper sulfide would enhance the formation of chromium oxide film which improve the pitting corrosion resistance in the H₂S–Cl⁻ environment.     

Liquid/solid contact mode of super-hydrophobic film in aqueous solution and its effect on corrosion resistance

Synthesised 3-undecyl-4-amino-5-mercapto-1,2,4-triazole (UAMT) was used to fabricate super-hydrophobic film on copper (Cu) using the one-step electrolysis method. The resultant layer formed from the alkyl-amino-mercapto-triazole-Cu(I) through precipitation mechanism. Super-hydrophobic film can contact with NaCl solution in two different modes (i.e., Cassie and Wenzel modes) depending on its immersion depth. Its corrosion protection mechanism varies with the contact mode. The film contacting with NaCl solution in the Cassie mode presents better protection effect due to the air trapped. It can remain stable within a wide potential range because of its excellent corrosion protection property and chemical stability.     

白铜基体低表面能复合膜的制备及其耐腐蚀性能研究

目的研究混合修饰构筑白铜超疏水表面的可行性及防腐性能。方法以白铜为基体,采用简单的化学刻蚀法,以硝酸银溶液作为刻蚀液,经肉豆蔻酸和十二硫醇的混合乙醇溶液修饰来制备超疏水白铜。采用接触角测量仪、XRD、FTIR、SEM、EDS对超疏水白铜表面性能和结构等进行了表征,并利用Tafel曲线和电化学阻抗谱研究低表面能复合膜的耐蚀性能。结果肉豆蔻酸和十二硫醇的疏水长链都组装到薄银层表面,其中肉豆蔻酸和薄银层的键合形式为双齿桥式复合模式,超疏水白铜表面形貌由微米级枝晶和纳米级乳突状结构组成,同时材料表面与水的接触角达到157.4°,表现出超疏水水平。此外,制备的超疏水白铜表面具有良好的化学稳定性和耐腐蚀性能,在水、有机溶液、3.5%Na Cl溶液中分别浸泡2 d,所有样品表面仍表现为超疏水水平。由Tafel极化曲线拟合参数计算可知,其缓蚀效率达到83.9%。结论以两种低表面能物质混合修饰来制备超疏水白铜表面的方法是可行且有效的,且该复合膜具有优良的耐腐蚀性能。     

带锈青铜表面超疏水薄膜的制备及防腐性能研究

目的 研究带Cu2O锈青铜表面超疏水薄膜的制备工艺及其防腐性能。方法 采用直接浸泡法,在带氧化亚铜锈层青铜试片表面制备了超疏水薄膜,通过单因素实验分别考察了正十二硫醇-十四酸混合溶液配比以及浸泡时间对超疏水膜层构建及耐蚀性能的影响,并采用接触角测试、电化学方法及表面分析手段对膜层性质、结构及稳定性进行了评价。结果 正十二硫醇和十四酸的疏水长链成功组装到带Cu2O锈青铜表面。混合溶液含5.0 nmol/L的正十二硫醇和1.0 nmol/L的十四酸,浸泡时间为1 h,是超疏水薄膜的最佳制备条件,此时表面接触角为157.2°,缓蚀效率高达97.21%。同时,电化学阻抗谱结果显示,电荷转移电阻相较于超疏水处理前增大了2个数量级,表明该膜层具有良好的耐蚀性能。该膜层在大气模拟液中浸泡30 d后,缓蚀效率仍有96.56%,说明其稳定性优异。结论 带Cu2O锈青铜表面构建的超疏水薄膜能够有效提高其耐腐蚀性和疏水性。     

Inhibiting properties of benzimidazole films for Cu(II)/Cu(I) reduction in chloride media studied by RDE and EQCN techniques

The effects of benzimidazole (BIM) and 2-methylbenzimidazole (MBIM) on the electroreduction of Cu(II) on a rotating Pt disk electrode in chloride media were investigated. These studies were undertaken in conjunction with earlier observation that these imidazole derivatives act as inhibitors of copper corrosion processes and are non-toxic. We have found that BIM and MBIM also form adsorption films on Pt, which are able to inhibit one-electron reduction of Cu(II) to Cu(I) and prevent the development of convective diffusion limiting current wave. The inhibition was found to be controlled by field-assisted mass transfer in the film. The ingress of Cu(II) species into the film was detected using the EQCN technique. The EQCN measurements indicate that small fraction of Cu(I) formed in the film by reduction of Cu(II) is retained in the film, most likely in the form of CuCl. The uptake of CuCl by inhibitor films diminishes in strongly inhibiting films (e.g., in acidic medium). The inhibition effectiveness of Cu(II) reduction process by Pt∣BIM and Pt∣MBIM films increases strongly with increasing acidity of the medium in the pH range from 3.0 to 1.0. The mechanism of this remarkable pH effect has been proposed. It is based on charge and pH-induced film restructuring, including changes in orientation and protonation of BIM molecules in the film.     

Super-hydrophobic film prepared on zinc as corrosion barrier

Potentiostatic electrolysis was carried out to prepare super-hydrophobic film on the surface of metallic zinc. The resultant film was examined by field emission scanning electron microscopy, Fourier transform infrared spectroscopy, electrochemical measurements, and contact angle test. The super-hydrophobic property of the film results from the air trapped among the sheets of zinc tetradecanoate. This air behaves as a dielectric for a pure parallel plate capacitor, thereby inhibiting electron transfer between the electrolyte and the substrate. The air can also enhance the contribution of the film itself to protection performance.     

具有超疏水表面的铜及铜合金耐蚀行为研究进展

随着铜及其合金的广泛应用,腐蚀问题也造成了巨大的社会和经济损失,超疏水表面处理是一种新型且非常有前景的金属防腐蚀方法。本文简要介绍了用于制备铜基超疏水表面的疏水材料和方法;重点分析了超疏水表面对铜及铜合金耐蚀性能的影响;归纳了超疏水表面防腐蚀的机理;总结了超疏水表面防腐蚀的技术障碍;最后提出了超疏水表面与缓蚀剂联合防腐蚀的新思路。     

Effects of blending on surface characteristics of copper corrosion products in drinking water distribution systems

Copper scales formed over 6-months during exposure to ground, surface and saline waters were characterized by EDS, XRD and XPS. Scale color and hardness were light red-brown-black/hard for high alkalinity and blue-green/soft for high SO₄ or Cl waters. Cl was present in surface or saline copper scales. The Cu/Cu₂O ratio decreased with time indicating an e transfer copper corrosion mechanism. Cu₂O, CuO, and Cu(OH)₂ dominated the top 0.5-1 A° scale indicating continuous corrosion. Cu₂O oxidation to CuO increased with alkalinity, and depended on time and pH. Total copper release was predicted using a Cu(OH)₂ model.     

Mechanistic studies of corrosion product flaking on copper and copper-based alloys in marine environments

The mechanism of corrosion product flaking on bare copper sheet and three copper-based alloys in chloride rich environments has been explored through field and laboratory exposures. The tendency for flaking is much more pronounced on Cu and Cu–4 wt%Sn than on Cu–15 wt%Zn and Cu–5 wt%Al–5 wt%Zn. This difference is explained by the initial formation of zinc and zinc–aluminum hydroxycarbonates on Cu15Zn and Cu5Al5Zn, which delays the formation of CuCl, a precursor of Cu₂(OH)₃Cl. As a result, the observed volume expansion during transformation of CuCl to Cu₂(OH)₃Cl, and concomitant corrosion product flaking, is less severe on Cu15Zn and Cu5Al5Zn than on Cu and Cu4Sn.     

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。     

Potent inhibition of copper corrosion in neutral chloride media by novel non-toxic thiadiazole derivatives

Inhibiting effect of two novel non-toxic thiadiazole derivatives on copper were investigated in 3.5% NaCl solution using weight loss and electrochemical measurements. Presence of inhibitors and increase of concentration greatly decrease corrosion rate, parameters determined from polarization curves and EIS plots show that inhibitors decrease both cathodic and anodic current densities, suppressing charge transfer process by adsorption on copper surface. Thermodynamic calculation indicates chemisorption obeys Langmuir isotherm. Surface layers were characterized by SEM coupled with EDX. Raman micro-spectroscopy reveals that inhibitor molecules suppress copper corrosion via formation of thiadiazole–Cu complex. Relationships between inhibition efficiency and molecular orbital were also evaluated.     

铜在含氯薄液膜和杂色曲霉作用下的腐蚀行为

目的 研究纯铜在含氯液膜和霉菌共同作用下的腐蚀行为与机理。方法 将海南文昌采集的一株野生杂色曲霉接种到质量分数分别为0.9%和3.5%的NaCl溶液中制成孢子悬浮液,将孢子悬浮液均匀喷洒到铜试样表面后进行恒温恒湿试验,试验不同周期后采用体视学显微镜、扫描电子显微镜观察铜试样的腐蚀形貌,采用X射线光电子能谱仪分析试验14 d的试样表面和氩离子刻蚀15 s后的成分。结果 纯铜在NaCl薄液膜下的腐蚀产物具有明显的双层结构,内层靠近基体的为致密的Cu2O钝化层,外层为疏松的Cu2(OH)2CO3和Cu2(OH)3Cl组成的Cu(II)碱式盐;无菌时,铜表面出现大量蓝绿色的Cu(II)碱式盐,杂色曲霉存在时,铜表面腐蚀产物主要为红棕色的Cu2O钝化膜,仅有少量Cu(II)碱式盐零星分布在Cu2O膜外层;0.9% NaCl薄液膜与霉菌共同作用时,试样表面腐蚀产物主要为Cu2O,当薄液膜中盐的质量分数升高到3.5%时,霉菌数量减少,Cu(II)碱式盐较0.9% NaCl薄液膜组增多。结论 纯铜的腐蚀产物由内层的Cu2O钝化层、外层的Cu2(OH)2CO3和Cu2(OH)3Cl组成双层结构。杂色曲霉通过呼吸作用影响液膜中的O2浓度进而影响铜的腐蚀产物组成,霉菌存在时腐蚀产物中Cu(II)碱式盐显著减少。含氯液膜与霉菌共同作用时,液膜中的NaCl浓度通过影响杂色曲霉的生长活性而影响腐蚀产物组成。     

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.     

阴极刻蚀法制备超疏水铝镀层及其抗腐蚀性能研究

对硅基磁控溅射铝镀层表面加载阴极电流,在镀层表面构建了微纳复合结构,并通过十四酸修饰获得稳定的超疏水膜。研究了超疏水表面的形成机制与结构特征,分析了超疏水表面的抗腐蚀性能。结果表明:经阴极刻蚀处理后,铝镀层表面形成了覆盖纳米级絮状物的腐蚀孔,呈现出珊瑚网状结构;再经十四酸有机修饰后,达到超疏水状态,十四酸在镀层表面形成了稳定的化学吸附,样品腐蚀阻效达到98.9%,抗腐蚀性能显著提高。     

Influence of hydrolysis time on the structure and corrosion protective performance of (3-mercaptopropyl)triethoxysilane film on copper

Films of (3-mercaptopropyl)triethoxysilane with different hydrolysis time were formed on copper surface. To evaluate the influence of hydrolysis time on structures and corrosion resistance of these films, Fourier-transform infrared spectroscopy, polarization curves, cyclic voltammetry and electrochemical impedance spectroscopy tests were performed on covered and uncovered copper specimens. Results indicate that the optimum hydrolysis time is 48 h. The film obtained in this case shows the best corrosion resistance in 3.5% (w) NaCl solution.     

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.     

Electrochemical behavior of a lead-free Sn–Cu solder alloy in NaCl solution

Electrochemical impedance spectroscopy (EIS), potentiodynamic polarization techniques and an equivalent circuit analysis are used to evaluate the electrochemical corrosion behavior of Sn–Cu alloy samples in a naturally aerated 0.5 M NaCl solution at 25 °C. It has been found that a better electrochemical corrosion resistance is provided by a coarser cellular microstructure array. It has also been found that the corrosion current density (i_corr) is of about a quarter when compared with that of the finest microstructure examined. Such behavior is attributed to both localized strains between the Sn-rich phase and intermetallic (IMC) particles and the cathode/anode area ratios. The effect of copper alloying on i_corr is also discussed.     

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.     

Formation of oxides on copper in alkaline solution and their photoelectrochemical properties

The anodic formation of Cu(I) and Cu(II) oxides on polycrystalline copper in a deaerated alkaline solution is studied using the technique of the synchronous recording of transients of the photocurrent and polarization current. The oxide formation in a currentless mode is analyzed via the synchronous recording of photopotential and corrosion potential. It is found that copper is susceptible to corrosion oxidation due to traces of dissolved oxygen with the formation of a Cu(I) oxide. The preliminary formation of the underlayer of anodic Cu(I) oxide on copper hinders its further corrosion oxidation. It is confirmed that copper oxides Cu₂O and CuO, which appear on copper in both anodic and corrosion modes of formation, are p-type semiconductors. The initial stage of anodic oxidation of copper is characterized by the formation of an intermediate compound of Cu(I), possibly CuOH, which exhibits n-type conductivity. A film of Cu(I) oxide is thin and has a band gap of 2.2 eV for indirect optical transitions. Anodic polarization in the range of potentials of CuO formation leads to the formation of a thicker oxide film, which is a mixture of Cu(I) and Cu(II) oxides.