带锈青铜文物材料在环境模拟介质中的腐蚀发展行为

目的研究3种带锈青铜及裸青铜文物材料在3种环境模拟液中的腐蚀发展行为。方法采用动电位扫描和SEM-EDS等方法研究试样的腐蚀特征和现象。结果在模拟大气环境介质中,电位在50~160 m V阳极极化范围内,与其他三种青铜材料相比,带CuCl锈青铜的阳极腐蚀电流密度最小;在模拟海水介质中,锈蚀青铜的腐蚀电流密度略大于裸青铜的;在模拟SO_2环境介质中,4种青铜试样的Rp值均大于大气环境介质中的。结论在模拟大气环境介质中,且阳极极化电位接近自腐蚀电位时,CuCl锈对青铜基体具有一定的保护性;在模拟海水环境介质中,带锈青铜的表面锈对基体没有保护作用;在模拟SO_2环境介质中,与在模拟大气环境介质中相比,SO_3~(2-)的引入会抑制青铜的腐蚀。表面形貌和能谱分析结果表明,裸青铜、CuCl锈青铜和混合锈青铜在模拟SO_2环境介质中,有点蚀现象发生,对粉状锈的生成有抑制作用。     

应用电化学方法原位研究薄液膜下青铜的大气腐蚀行为(英文)

采用阴极极化曲线、开路电位和电化学阻抗谱,监测青铜在不同薄液膜厚度下的大气腐蚀行为。阴极极化曲线结果表明,阴极极限电流密度随着液膜的减薄而增大。电化学阻抗谱结果表明,在腐蚀初期,腐蚀速率随着液膜的减薄而增加,这主要是由于腐蚀速率是由阴极过程控制的;随着时间的延长,腐蚀程度随着液膜厚度的变化从强到弱的趋势为:150μm,310μm,100μm,本体溶液,57μm。开路电位和电化学阻抗谱实验较好地再现了原位电化学腐蚀信息,且电化学结果与物理表征具有良好的一致性。     

Effect of direct current electric field on atmospheric corrosion behavior of copper under thin electrolyte layer

A thin layer electrochemical cell was successfully developed to study the atmospheric corrosion behavior of copper film in printed circuit board (PCB-Cu) under thin electrolyte layer (TEL) and direct current electric field (DCEF) by electrochemical impedance and electrochemical noise analysis. The electrochemical measurements and SEM morphologies after corrosion test indicate that DCEF decreases the corrosion of PCB-Cu under TEL. The corrosion rate and probability of pitting corrosion of PCB-Cu under DCEF decrease due to the electric migration of aggressive Cl⁻ ion out of working electrode surface.     

我国西部地区大气环境腐蚀性及材料腐蚀特征

我国西部地区地形、地貌复杂、气候多变，按气候因素及环境条件，大致可分为酸雨、沙漠、高原和热带雨林4大类典型大气环境．各类环境的大气腐蚀严酷性是不同的．不同环境类型对材料的腐蚀(老化)破坏特点也不一样．酸雨大气明显加剧了金属、金属保护性涂(镀)层、建筑材料等的腐蚀破坏、沙漠大气环境虽然干燥、少雨，但对处于塔里木盆地的塔克拉玛干沙漠地区，由于空气尘降物中的盐类物质较高，Cu、Zn、Al、不锈钢及金属涂层的腐蚀破坏比中、东部的湿热、亚湿热城市大气反而严重．在高原环境下，高分子材料的迅速老化破坏是其显著特征、热带雨林大气环境的特点主要表现在光学仪器、皮革、织物、木材等的严重霉变．     

油套管N80钢的乙酸腐蚀行为

模拟油气田环境,采用高温高压釜对油套管N80钢进行失重腐蚀试验.结果表明:N80钢的腐蚀速率随着乙酸浓度的增加呈升高趋势,但在乙酸浓度为3000μl/L时反而比在1000μl/L时低,并且其在含乙酸的腐蚀介质中的腐蚀速率远高于在未含乙酸的腐蚀介质中的腐蚀速率.利用扫描电子显微镜(SEM)、能散X射线谱仪(EDS)和X射线衍射技术(XRD)研究了在不同乙酸浓度条件下油管钢N80腐蚀的特征并讨论了其腐蚀机理.     

Influences of NH4 + ions and thin electrolyte layers (TEL) thickness on the corrosion behavior of AZ91D magnesium alloy

In this study, the influences of NH₄ ⁺ ions and the thin electrolyte layer (TEL) thickness on the corrosion behavior of the AZ9D magnesium alloy in NH₄⁺‐containing environments were investigated by electrochemical measurements and surface characterization. The experimental results indicate that NH₄⁺ greatly accelerates the corrosion of AZ91D magnesium alloy whether in a bulk solution or in a TEL. As the TEL thickness decreasing, the corrosion resistance of the AZ91D magnesium alloy is strengthened. According to the corrosion morphology, electrochemical analysis, and characterization analysis of corrosion products, the corrosion mechanism of AZ91D under TELs with different thicknesses is divided into three stages: (a) uniformly distributed corrosion pits with deep depth and large size when TEL thickness is higher than or equal to 500 μm; (b) slightly corrosion with randomly distributed corrosion pits and the accumulation of small amount of corrosion product when TEL thickness is between 100 μm and 200 μm; (c) no corrosion pit with only deposition of corrosion product when TEL thickness is lower than or equal to 100 μm. Among which, the roles of NH₄⁺, TEL thickness, and corrosion product are emphasized and discussed in the corrosion process of AZ91D magnesium alloy under TEL with different thicknesses.     

锡青铜化学镀 Ni-P 合金工艺及镀层性能

目的在锡青铜基体上化学镀Ni-P合金镀层,提高锡青铜的耐磨性和耐腐蚀性。方法以酸性含锌活化液活化锡青铜试样,在相同的条件下实施化学镀,并对镀态试样进行不同温度(250,400,500℃)下的热处理。对比基体、镀态试样和热处理试样的性能,研究热处理温度对锡青铜化学镀Ni-P合金层微观结构、显微硬度、耐磨性和耐腐蚀性的影响。结果锡青铜表面形成了Ni-P合金镀层,并且镀层无孔隙缺陷,与基体结合良好,沉积速率较快,为10.00μm/h。经热处理后,镀层的微观结构由非晶态向晶态转变,在500℃热处理的镀层显微硬度最大,耐磨性最好。镀态镀层和经250℃热处理的镀层在10%HNO3溶液和10%H2SO4溶液(10%均为体积分数)中的耐腐蚀性明显好于锡青铜基体,镀态镀层在两种介质溶液中的腐蚀速率分别为0.225,0.146 mg/(cm2·d)。结论采用酸性含锌活化液活化锡青铜基体,可以在锡青铜表面制备出化学镀Ni-P合金镀层,且镀覆效果较好。这表明紫铜化学镀Ni-P合金工艺同样适用于锡青铜。     

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。     

高温含杂醋酸环境中设备选材的探讨

对接触高温醋酸生产装置腐蚀行为及其选材进行了讨论.提出了醋酸对材料的腐蚀,既要考氧的影响,也不能忽视杂质的作用;对铜、不锈钢、钛三种材料作为高温醋酸塔器用材进行了评价比较.     

Korrosionsschäden an Bronzeplastiken

Corrosion damage of bronze sculptures In order to assess the effect of contaminated air (industrial and urban atmospheres) on bronze sculptures the composition of the base metal and of the corrosion products has been investigated pn a number of sculptures in the open air. in addition to the corrosion products typical of bronze — basic copper sulfate, basic copper nitrate, basic copper chloride stannous acid, lead sulfate — other compounds have been found which — as e.g. gypsum — are formed by reaction between dust and atmospheric contaminats. The corrosion layers usually include several strata; soot containing strata are characteristic of the winter season. Oils, waxes and plastic coating are suitable agents for protecting bronze sculptures against corrosion. The two first mentioned materials are suitable in particular for older bronzes having a natural or artificial patina; they require, however, renewal after regular intervals; plastic coatings are suitable for application to bright metal surfaces and are more durable. Despite the high manpower requirement it is advisable regularly to clean the sculptures with detergent containing water.     

Corrosion behavior of copper,tin, and bronze CuSn14 in acid rain solution

The corrosion behavior of copper, tin, and bronze CuSn14 is studied in simulated acid rain (pH 4.5) by electrochemical techniques, cyclic voltammetry and electrochemical impedance spectroscopy. The potentiodynamic formation of anodic oxide film on copper and tin is described in terms of high-field model. Cyclic voltammetry shows that dissolution of bronze is higher than of pure copper metal in acid rain. Electrochemical impedance spectroscopy data reveal that oxide films formed on copper and tin have a higher resistance and suppressed diffusion process through the surface layer than the oxide film formed on bronze CuSn14 at the same conditions.     

Comparison of the corrosion behavior of copper tubes in formic acid and acetic acid environment

Carboxylic acids with different carbon chains have different corrosion behaviors on copper tubes. In this paper, corrosion behavior and corrosion mechanisms of copper tubes in formic acid (HCOOH) and acetic acid (CH₃COOH) were analyzed by vapor corrosion tests, electrochemical tests, contact angle examination, optical microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. The corrosion process of copper tubes in the HCOOH environment is more complex than in the CH₃COOH environment and HCOOH is easy to cause “ant nest” corrosion on copper tubes. The corrosion rate is faster and the surface of the copper tube is more easily corroded in the CH₃COOH environment due to the formation of unstable and loose corrosion products, Cu(OH)(CH₃COO)₂·2H₂O. The results of the contact angle examination showed that the contact angles of HCOOH and CH₃COOH on copper tube surface were 25° and 9°, respectively, which means that CH₃COOH is more likely to be absorbed by the surface of the copper tube evenly. Differences in the wettability of these two carboxylic acids with copper tubes are the main reason for the different corrosion phenomena. The corrosion mechanisms of copper tubes in carboxylic acid are also discussed.     

Corrosion behaviour of copper under chloride-containing thin electrolyte layer

The corrosion behaviour of copper under chloride-containing thin electrolyte layers (TEL) was investigated using electrochemical impedance spectroscopy (EIS), cathodic polarization, linear polarization, SEM/EDS and XRD. The results indicate that the copper corrosion rate increases as TEL thickness decreases during the initial stages. After 192 h of immersion, the corrosion rate of copper under TEL in this order: 300 > 402 > 199 > bulk solution > 101 μm. The corrosion behaviour is uniform under TEL, and pitting is the primary corrosion type in the bulk solution. A corrosion model of the behaviour of copper under chloride-containing TEL is proposed.     

海洋大气环境下镁合金腐蚀行为研究进展

本文综合研究了海洋大气环境下镁合金腐蚀行为的研究进展,比较分析了各种因素对腐蚀行为的影响,对当前研究进展进行总结并对未来研究方向进行展望。在海洋大气环境下,表面薄电解质溶液膜的包覆是镁合金发生电化学腐蚀的主要原因,且多发生局部腐蚀。相比于内陆大气环境,海洋大气中含有较多无机盐气溶胶颗粒,导致点蚀成为主要的局部腐蚀形式。相对湿度的升高会导致薄电解质膜厚度增加,进而加速整体腐蚀速率。随气温上升,镁合金的大气腐蚀速率线性增加,而空气中的CO₂可以抑制NaCl对镁合金的侵蚀。该领域未来需更多关注具体使役环境下合金的腐蚀机理,以及各种环境因素对腐蚀行为的协同作用机制,以指导海洋用镁合金材料的设计和制备。     

山西博物院馆藏青铜器的锈蚀产物分析

目的对山西博物院馆藏大量珍贵青铜器的锈蚀情况进行分析,为后续的保护修复提供科学依据和数据支持。方法选用21件山西省出土的馆藏青铜器,通过超景深显微镜、偏光显微镜、拉曼光谱分析等手段,对青铜器物表面锈蚀物进行综合分析,确定有害锈蚀物。结果这批青铜器表面锈层结构有5类,绿色锈蚀物主要为孔雀石、氯铜矿,其中氯铜矿为青铜器有害锈蚀的主要成分,少量绿色锈蚀物为斜氯铜矿、水胆矾,红色锈蚀物为赤铜矿,蓝色锈蚀物为蓝铜矿。结论青铜器表面的孔雀石锈蚀物大多结构致密,对青铜器本体无害,还可阻隔铜与空气、水分等物质的直接接触,对器物具有一定的保护作用,可以保留。氯铜矿对青铜器的保存具有隐患,在修复中应对其彻底清除。     

Effects of electrolyte thickness,chloride ion concentration,and an external direct current electric field on corrosion behaviour of silver under a thin electrolyte layer

ABSTRACT

Effects of electrolyte thickness, chloride ion concentration, and an external direct current electric field (DCEF) on the corrosion behaviour of silver under a thin electrolyte layer (TEL) were investigated using electrochemical and surface techniques. The results indicate the corrosion rate of silver increases with the decrease of TEL thickness and the increase of chloride ion concentration. Moreover, an interesting conclusion was drawn that the corrosion rate of silver near the positive plate of DCEF first increases and then decreases with the increase of electric field intensity. In a DCEF, different polarisation behaviours of silver at different positions were attributed to the differences of the local corrosion environment.     

The atmospheric corrosion of quaternary bronzes: The action of stagnant rain water

The corrosion behaviour of a quaternary bronze UNS C83600 exposed to stagnant acid rain was examined through wet-dry tests. During the tests, parallel monitoring was performed to determine the evolution of both the bronze surface and the weathering solution composition. The results show that the kinetics of bronze oxidation is governed by diffusion through a two-layer patina: an inner Sn-rich layer and an external Cu and Pb-rich layer. The corrosion rate of the alloy decreases with time, but the dissolution of individual metals (Cu, Zn and Pb) in the environment increases with different trends, showing progressive patina destabilisation.     

Evaluation of the anticorrosive properties of benzotriazole alkyl derivatives on 6% Sn bronze alloy

This paper focuses on the anticorrosive behaviour of surface films formed by different benzotriazole alkyl derivatives on a Cu6Sn bronze (B6), whose composition is similar to materials used for outdoor artefacts. Some alkyl derivatives of the 1,2,3-benzotriazole (BTA) as: 5-hexyl-1,2,3-benzotriazole; 5-dodecyl-1,2,3-benzotriazole and [5-(1-undecyl)dodecyl]-1,2,3-benzotriazole were synthesized in order to investigate the influence exerted by the aliphatic chain on the inhibiting properties of the base molecule (BTA) toward bronze corrosion. The protective efficiency of the organic films, after a preliminary evaluation by electrochemical measurements, was determined by thin layer activation (TLA) and gravimetric techniques on the samples submitted to artificial weathering experiments in acid rain. For TLA measurements a γ-emitting radio nuclide ⁶⁵Zn (t_1/2 = 244 days), used as a corrosion tracer, was produced on the bronze surface by a high energy proton beam. At the end of artificial weathering exposures the radioactivity recovered on the bronze surface, once it was treated with a picking solution, allowed determination of the thickness loss. All the results arising from the different techniques, used in this study, show that BTA molecules bearing long aliphatic chain act as the best corrosion inhibitors.     

钛,铜和不锈钢在醋酸中的腐蚀行为

评述了金属在无氧醋酸，含氧醋酸中的腐蚀机理，叙述了铜，钛和不锈钢在醋酸介质中的腐蚀行为；讨论了醋酸介质中的耐蚀选材。     

Multianalytical in situ investigation of the initial atmospheric corrosion of bronze

Atomic force microscopy (AFM) and infrared reflection absorption spectroscopy (IRAS) were used for in situ investigations of the initial atmospheric corrosion of bronze. In addition ex situ XPS investigations were carried out on the samples before and after the exposure, as well as on the sputtered bronze sample. Investigations were carried out in synthetic air with 80% relative humidity (RH) and synthetic air with 80% RH with 250 ppb SO₂. At 80% RH, small features covering the surface were observed with AFM, whereas IRAS detected that more water is adsorbed on the bronze sample surface compared to pure copper. Large features on top of smaller features were observed with AFM on the bronze surface exposed to SO₂-containing humidified air. These large features were identified as copper sulfite. Furthermore, cuprous oxide was detected approximately 500 min after the introduction of SO₂. This fact and the XPS results indicate the formation of a protective lead oxide layer already during the preparation of the sample, which is destroyed by the SO₂-containing environment and leads to the formation of cuprous oxide and copper sulfite.