Electrochemical techniques applied to the conservation of archaeological metals from Spain: a historical review

The conservation and restoration of archaeological metals is one of the most complex conservation issues. Therefore, conservators usually employ the most advanced techniques, with the purpose of obtaining positive results for the preservation of the objects. One of the aims of conservation treatments is avoiding the reactivation of corrosion processes. Electrochemical treatments applied on archaeological metals were employed in Spain since the beginning of the twentieth century. During its history, the treatments were praised and reviled, practiced and discontinued. Conservation criteria have also exerted an influence over electrochemical treatments. Nowadays, electrochemical techniques are provided with control devices, such as potentiostatic control and could be considered again as a very valuable option, in combination with traditional and vanguard techniques, to recover the archaeological metallic heritage.     

Use of EIS for the evaluation of the protective properties of coatings for metallic cultural heritage: a review

The best way to reduce the degradation of metallic cultural heritage is through preventive conservation measures but, in many cases, it is not possible to obtain adequate environmental conditions, and it is necessary to apply coatings to the artefacts in order to protect them against corrosion. There is a continuous search in the metal conservation community for new and improved coatings that provide a better protection to the objects whilst respecting the special requirements of the conservation–restoration ethics. Whilst electrochemical techniques have a long tradition in conservation–restoration treatments for metallic cultural heritage, the evaluation of protective coatings using electrochemical impedance spectroscopy (EIS) has only been used very recently. EIS is a very well-established method to investigate metal coatings for general purposes and has many advantages that make it especially suitable for testing coatings for metallic works of art. This paper makes a review of the use of EIS for testing coatings for metallic cultural heritage from the first publications in the mid-1990s to the last papers. The experimental setup used, the types of coatings and metals investigated and the interpretation of the results are reviewed and compared with the use of EIS for testing general purpose anti-corrosive coatings.     

Voltammetric methods applied to identification, speciation, and quantification of analytes from works of art: an overview

Voltammetry of microparticles, an electrochemical methodology based on the record of the voltammetric response of sparingly soluble solids mechanically transferred to the surface of inert electrodes in contact with suitable electrolytes, is able to provide significant analytical information in the fields of conservation and restoration of cultural goods. Using this methodology, identification, speciation, and relative and absolute quantification of analytes from works of art samples can be achieved. Applications to the analysis of organic and inorganic pigments in paints, fibbers, ceramic materials as well as alteration compounds in paintings and metallic artifacts are reviewed.     

Electrochemistry for conservation science

Voltammetry of microparticles, an electrochemical methodology based on the record of the voltammetric response of sparingly soluble solids mechanically transferred to the surface of inert electrodes in contact with suitable electrolytes, is able to provide significant analytical information in the fields of conservation and restoration of cultural goods. Using this methodology, identification, speciation, and relative and absolute quantification of analytes from works of art samples can be achieved. Applications to the analysis of organic and inorganic pigments in paints, fibbers, ceramic materials as well as alteration compounds in paintings and metallic artifacts are reviewed.     

青铜器文物腐蚀受损原因的研究

以三千多年前商周时代为代表的青铜器是我国金属质地文物中的珍品。本文调查了青铜病的发现‘症状’,对青铜病形成的过程和原因,以小孔腐蚀原理研究了溶液的ＰＨ值和Ｃｌ＾－浓度对青铜腐蚀的影响,进行了模拟闭塞电池内化学和电 化学状态的研究,提出出青铜病的产生机理并探讨符合文物保护要求的青铜器保护处理方法。     

Electrochemical characterisation of dental alloys: its possibilities and limitations

Dental alloys are metallic biomaterials which have a broad variation of composition compared to technical alloys. It is therefore in the interest of patients and technicians to conduct a good assessment of the electrochemical behaviour of dental alloys in order to collect information about their corrosion resistance. The purpose of this work was to demonstrate possibilities and limitations of two electrochemical techniques: the voltammetry of immobilised microparticles (ViMP) onto lead, and cyclic voltammetry measurements with the help of the mini-cell system (MCS). Based on fingerprints obtained from ViMP it was possible to analyse and differentiate the dental alloys. The results obtained by MCS were comparable with ViMP, but give a better understanding of the corrosion behaviour of the materials.     

Evaluation of corrosion behaviour of selected metallic samples by electrochemical noise measurements

Electrochemical noise (EN) denotes spontaneous fluctuations in potential and current originating from the corrosion processes. In this work, EN was measured for three model metallic materials of known corrosion properties: Al, Fe and Fe30Al. Corrosion behaviour was assessed in neutral, acidic or alkaline solutions containing 4 wt% NaCl. Correlation between the electrochemical noise and corrosion intensity was established on the basis of appropriate treatment of the recorded numerical data and ex situ examination of the specimen surface. The parameter, referred to as EN resistance, allowed relatively simple and rapid evaluation of the corrosion behaviour of the investigated metallic materials.     

Analytical Techniques Applied to the Study of Industrial Archaeology Heritage: The Case of Plaiko Zubixe Footbridge

In this work, micro-Raman spectroscopy and micro-energy-dispersive X-ray fluorescence spectroscopy (µ-EDXRF) were applied on microsamples taken from the Plaiko Zubixe footbridge (1927) located in Ondarroa (Basque Country, Spain) in order to investigate the original paint coating and make an evaluation of the conservation state before its restoration. Elemental and molecular images were acquired for the study of the compounds distribution. Some modern pigments such as phthalocyanine blue and green pigments, minium, calcium carbonate, Prussian blue, and hematite were identified. Barium sulfate and titanium dioxide were recognized as opacifier agents. Thanks to the study of the stratigraphies, it has been possible to determine the original paint layer, which includes lead white, ultramarine blue, carbon black, and barium sulfate. In addition, colorimetric analyses made it possible to know the CIELab values of the original layer in order to reproduce the original colour during the planned restoration work. The massive presence of chlorine detected by µ-EDXRF and the corrosion products of the rust layer, in particular akaganeite and hematite, highlighted the atmospheric impact in the conservation of the bridge because they were due to the effect of both marine aerosol and to the presence of acidic components in the environment coming from anthropogenic activity. This work demonstrated the usefulness of a scientific approach for the study of industrial archaeology heritage with the aim to contribute to its conservation and restoration.     

ITO在NaOH溶液中阳极与阴极极化过程的电化学行为

通过循环伏安法等方法研究了氧化铟锡(ITO)透明导电薄膜的电化学行为. 获得了ITO薄膜在NaOH溶液中阴极和阳极极化处理前后的循环伏安曲线. 采用透射光谱, 方块电阻测试, 扫描电子显微镜(SEM), 能量色散X射线荧光光谱(EDS)与X射线衍射(XRD)表征ITO薄膜经电化学处理后的反应产物. 结果表明, ITO薄膜在阳极处理后(约为+1.5 V(vs SCE))保持了稳定的成分和结构. 但经阴极处理后(约为-1.5 V(vs SCE))发生了严重的电化学腐蚀, 可见光透射率大幅下降, 方块电阻增加一个数量级. 经SEM、EDS和XRD表征分析, 证明阴极处理过程使ITO薄膜中的In3+还原成了In单质.     

Electrochemical characterization of organic coatings for protection of historic steel artefacts

Electrochemical techniques are mainly known in the field of cultural heritage conservation as a tool for the elimination of corrosion layers or the removal of chlorides. However, these techniques are also a valuable tool for assessing the anti-corrosive efficiency of protective coatings. The aim of this study was to evaluate the performance of different coatings for their use in metallic heritage conservation using polarisation resistance (R _p) and electrochemical impedance spectroscopy (EIS). Carbon steel samples were prepared to simulate the surface composition and morphology of historic steel artefacts, and coated by a conservator–restorer following the common practices in conservation treatments. Three commercial organic coatings have been studied: a microcrystalline wax (Renaissance™) and a methyl acrylate/ethyl methacrylate copolymer resin (Paraloid™ B-72) dissolved in acetone—both them commonly used in conservation and restoration treatments—and an ethylene copolymer wax emulsion in water (Poligen™ ES-91009) that has not been used so far for this purpose. Four commercial corrosion inhibitor additives were added to the Paraloid™ B-72 resin and Poligen™ ES-91009 wax. The additives were commercial preparations with the following known active components: a blend of triazoles (M435), an ammonium salt of tricarboxylic acid (M370), a calcium sulphonate (M109), and a bis-oxazoline (Alkaterge-T™). R _p and EIS results showed that the best protection of the steel specimens was afforded by Poligen™ ES-91009 when applied in thick layers. None of the additives have shown a clear improvement of the protection properties of the coatings, and one of them impaired the barrier effect of the coating.     

Introducing a novel bacterium,Vibrio neocaledonicus sp., with the highest corrosion inhibition efficiency

Degradation of metals due to corrosion causes serious economic problems throughout the world, and different corrosion protection techniques are being used to extend the service life of metallic structures. It has been suggested that some microorganisms can inhibit electrochemical corrosion of metals. Here we isolated a new marine inhibitory bacterium, Vibrio neocaledonicus sp., and EIS results showed that the corrosion resistance of carbon steel increased by more than sixty fold in the presence of this bacterium. This is the highest corrosion inhibitory effect reported for bacteria and is comparable with some industrial coatings such as electroless Ni. This bacterium affected corrosion by the formation of an inhibitory layer on the metal surface in the first hours of attachment, with the consumption of oxygen by electron transport proteins. Extracellular polymeric substances produced by this bacterium also have a corrosion inhibitory effect. Thus we propose a new, natural, non-toxic, and cost-effective system for controlling corrosion processes using this bacterium or extracellular polymeric substances produced by this bacterium.     

Study of anodizing process on aluminium foam to improve the corrosion behavior

Aluminium foam is obtained by the production of air into metallic melt. This material shows a very low density together with good mechanical properties, high impact energy absorption, and fire resistance. Different production ways to obtain metallic foam are possible. Considering the cost, the Alporas process is particularly interesting. By means of this production method, a block of metallic foam with close cells is obtained. By slicing, foam panels are obtained. The mechanical cut promotes the formation of an open cells texture on the surface. In this last case, the complex morphology of aluminium foam could be a critical point considering the corrosion behavior in aggressive environments, where localized corrosion phenomena, as pitting or crevice corrosion, are likely to occur. The anodizing treatment is one of the most used methods to improve the corrosion resistance of aluminium and aluminium alloys. The aim of this paper is to perform an anodization treatment to enhance the corrosion resistance of aluminium foam. Constant voltage anodization (12 V for 60 min) and pulsed current anodization (0.04 A/cm² for 60 seconds and 0.01 A/cm² for 15 seconds, repeated for 15 cycles) have been carried out in 15 wt% H₂SO₄ at 20°C. The anodized samples are observed in cross section by optical and electronic microscopes to investigate the structure of the anodic oxide layer and the presence of defects and to measure the thickness of the layer. The corrosion protection performance and the compactness of layers are evaluated using acetic salt spray test and electrochemical impedance spectroscopy.     

电化学STM技术在金属腐蚀科学中的应用及研究进展

本文介绍了电化学STM在金属腐蚀电化学研究领域的技术优势.其最大特点是可以在金属腐蚀环境中和原子/分子水平上,实时、原位、三维空间观察,并可以通过电位控制表面电极过程.综述了电化学STM在钝化膜结构、缓蚀剂的自组装膜、金属表面原子的活性溶解等揭示腐蚀缓蚀机理的研究领域中所起的重要作用以及最新研究进展.     

Study of the mechanism action of sodium gluconate used for the protection of scale and corrosion in cooling water system

This work based on the mechanism action study of sodium gluconate (SG) for ordinary mild steel used for cooling water system treatment. In the first time, we evaluated the temperature effect on the scale inhibition of SG using statistic scale inhibition method. Result showed that the inhibition efficiency became more important with increasing temperature, at great concentration (10⁻² and 10⁻³ M). This can be explained by forming of stable complex SG–Ca²⁺. In the second time, the present work focuses on the study of operational parameters and corrosion products effect on SG performance using potentiodynamic polarization and electrochemical impedance spectroscopic method. The obtained results show that SG is a very good inhibitor for corrosion and scale and remains effective in the presence of corrosion products. For this study we were proposed a mechanism action for SG on metallic surface. In addition, the SG keeps its effectiveness in a more aggressive medium such as 3% NaCl. Finally, to complete the formulation, we added a not oxidizing biocide (CTAB) to SG. The results obtained show that SG remains its effective.     

硫酸根离子对铁在弱碱性溶液中阳极溶解和钝化行为的影响

采用浸泡实验, 电化学测试和表面分析技术研究了硫酸根离子浓度对铁在稀碳酸氢钠溶液中开路状态和阳极极化行为的影响. 在无硫酸根离子及含有少量硫酸根离子的碳酸氢钠溶液中, 铁的开路电位约为(-0.225±0.005) V, 并呈现钝化状态, 其电化学阻抗很大, 腐蚀速率较低. 在含有较高浓度硫酸根离子的碳酸氢钠溶液中, 铁的开路电位为(-0.790±0.010) V并呈现活性溶解状态, 其电化学阻抗较小, 腐蚀速率较高, 同时阳极极化曲线上能观察到活化-钝化转变现象. 由于铁在含有较高浓度硫酸根离子的碳酸氢钠溶液中处于活化状态, 阳极极化曲线上存在数个电流峰. 足够高的硫酸根离子浓度会导致铁表面预先形成或转变而成的氧化膜失效. 相比于自然曝氧状态, 在除氧条件下较低的硫酸根离子浓度即可引起铁在碳酸氢钠溶液中由钝态向活性溶解态的转变.     

The Influence of Doping Levels and Surface Termination on the Electrochemistry of Polycrystalline Diamond

The influence of surface chemistry and boron doping density on the redox chemistry of Fe(CN) at CVD polycrystalline diamond electrodes is considered. It is demonstrated that for this couple both the doping density and the surface chemistry are important in determining the rate of charge transfer at the electrode/electrolyte interface. For hydrogen terminated CVD diamond metallic electrochemical behavior is always observed, even at boron doping densities as low as 7×10¹⁸ cm^?3. In contrast, the electrochemical behavior of oxygen terminated CVD diamond varies with doping density, a metallic response being observed at high doping density and semiconductor behavior at low doping density. It is shown that the results attained may be explained by a surface state mediated charge transfer mechanism, thus demonstrating the importance of controlling surface chemistry in electroanalytical applications of diamond.     

Nitride layers on uranium surfaces

Uranium as an important energy material plays a significant role within the field of material sciences and nuclear industrial applications. However, metallic uranium is chemically active in ambient environment and is easily oxidized and corroded, leading to not only deterioration of its properties and failure of performance as working components but also nuclear pollution of the environment. Therefore, the development of corrosion protection systems for metallic uranium is an issue of prime importance. In view of the nitridation technology in Ti and Fe-based alloys, the successful application to improve the surface wear hardness and corrosion resistance, several nitridation methods have been developed for the surface modification of metallic uranium. Many studies have shown that the surface nitridation of metallic uranium can efficiently improve its corrosion resistance. The surface oxidation layer thickness is as thin as several nanometers even if placed 4?years in the atmosphere. At the present, nitridation of uranium surface is considered as the most promising surface modification way to protect uranium from corrosion. To design and fabricate nitride layers on uranium surface with reliable long-term protective effects, however, one needs deep understanding on the relationships among the physical and chemical properties of the nitride layers, the composition and structure of the layers, and the dependence on the techniques and the processing parameters. One also needs deep understanding on the corrosion behavior of the prepared nitride layers in the environment, and the related corrosion mechanism.In this review, we bring to the readers the achievements and recent advances on the uranium nitridation in the world, including the processing techniques and the related studies on the formation mechanism of the nitride layers, and the understanding on the property-processing-corrosion performance relationship of the layers, aiming at the development of high-performance resistance layers for metallic uranium by the surface nitridation technique. In the review (1) the surface nitridation techniques developed recently, the relationship between the preparation parameters and the composition as well as the structure of the surface layer are summarized; (2) the fundamental physical properties of the uranium nitrides are summarized, depicted and discussed; (3) the influence of the nitrides structure and composition and of the environment on resistance to corrosion as well as the formation mechanism of corroded products in oxidizing environments are depicted and discussed; (4) the potential application of uranium nitrides in other application field such as the application of thermal-electrical conversion is also discussed. Finally, the prospective on the investigations of nitride layers is suggested.     

In-situ Study the Corrosion Degradation Mechanism of Tinplate in Salty Water by Scanning Electrochemical Microscopy

In this work, the corrosion degradation of tinplate in contact with salty water is investigated by scanning electrochemical microscopy (SECM) electrochemical impedance spectroscopy (EIS). Experimental results indicate tin maintains at passive state during the exposure; however, pores and defects existed in tin coating leads to an exposure of carbon steel substrate to the electrolyte, in which localized corrosion tends to occur within the pore. A phenomenological model is proposed to interpret corrosion mechanism of tinplate in contact with salty food based on the proposed electrochemical equivalent circuit.     

Facile Electrochemical Method for the Fabrication of Stable Corrosion-Resistant Superhydrophobic Surfaces on Zr-Based Bulk Metallic Glasses

Both surface microstructure and low surface energy modification play a vital role in the preparation of superhydrophobic surfaces. In this study, a safe and simple electrochemical method was developed to fabricate superhydrophobic surfaces of Zr-based metallic glasses with high corrosion resistance. First, micro–nano composite structures were generated on the surface of Zr-based metallic glasses by electrochemical etching in NaCl solution. Next, stearic acid was used to decrease surface energy. The effects of electrochemical etching time on surface morphology and wettability were also investigated through scanning electron microscopy and contact angle measurements. Furthermore, the influence of micro–nano composite structures and roughness on the wettability of Zr-based metallic glasses was analysed on the basis of the Cassie–Baxter model. The water contact angle of the surface was 154.3° ± 2.2°, and the sliding angle was <5°, indicating good superhydrophobicity. Moreover, the potentiodynamic polarisation test and electrochemical impedance spectroscopy suggested excellent corrosion resistance performance, and the inhibition efficiency of the superhydrophobic surface reached 99.6%. Finally, the prepared superhydrophobic surface revealed excellent temperature-resistant and self-cleaning properties.     

Corrosion and biological behavior of nanostructured 316L stainless steel processed by severe plastic deformation

Nanostructured metals have different mechanical, chemical, and physical behaviors in comparison with the microstructured ones. Numerous research studies demonstrated that the biological behavior of nanostructured metallic implants was improved significantly. Concerning the nanostructured metals, decreasing the corrosion rate and the releasing of hazardous ions from metallic implants, and thus increasing the biocompatibility of implants are due to improving the native oxide layer. In the present study, nanostructured 316L stainless steel (biomedical grade) was manufactured via equal channel angular pressing (ECAP) method. To do so, the 316L stainless steel (SS) was exposed to the ECAP operation for eight passes. The impact of the ECAP process on corrosion behavior of SS samples was evaluated through performing the electrochemical polarization corrosion tests in Ringer's solution. Scanning electron microscopy was employed to study the surface morphology of common SS and ECAPed SS sample after the electrochemical polarization tests. Moreover, the biological behavior of the samples was evaluated via cell culture using fibroblast cells. The corrosion test results revealed a substantial decrease of corrosion rate from 3.12 (coarse‐grained sample) to 0.42 μA cm^?2 (for nanostructured). Furthermore, the cell proliferation in the interface of nanostructured sample and cell culture medium enhanced dramatically compared with the coarse‐grained one. The much better biological behavior of nanostructured SS sample in comparison with the coarse‐grained one is mostly due to the significant decrease of corrosion rate on the surface of SS samples, and the presence of much more chrome oxide on the surface of SS sample. Copyright © 2015 John Wiley & Sons, Ltd.