空间分辨电化学技术用于研究金属局部腐蚀

综合介绍我们已建立的具有微米空间分辨度的电化学方法,主要包括多种扫描微电极技术,并用于研究金属表面和金属／溶液界面电化学不均一性及局部腐蚀破坏过程。结果表明,这些空间分辨电化学方法的发展及应用,有助于深化对金属表面和金属／溶液界面电化学不均一性,特别是金属局部腐蚀发生、发展过程机理的认识。     

Nanoporous oxide formation by anodic oxidation of Nb in sulphate–fluoride electrolytes

The influence of hydrofluoric acid (HF) concentration and applied potential on the processes of anodic oxidation of Nb in sulphuric acid solution was studied by chronoamperometry, electrochemical impedance spectroscopy and scanning electron microscopy. During the first stage of the process, a compact barrier film is formed. On top of this film, a porous overlayer starts to form, then the nanopores grow into an ordered nanostructure. Subsequently, secondary 3D flower-shaped structures begin to form. These structures gradually spread all over the surface as an irregular multilayer film. The rates of the process of porous overlayer formation and subsequent growth of nanopore arrays increase with applied potential as well as with the HF concentration. The films have been characterised ex situ by electrochemical impedance spectroscopy at open circuit potential and capacitance vs. potential measurements to follow the different stages of nanoporous film formation with electrochemical methods. The impedance spectra and capacitance vs. potential curves have been interpreted using previously proposed models for the amorphous semiconductor/electrolyte interface. An attempt to rationalise the mechanism of nanoporous layer growth is presented by using the conceptual views of the mixed-conduction model and recent ideas for porous film formation on valve metals.     

Corrosion and passivity of metals in methanol solutions of electrolytes

Electrochemical and corrosion behaviour of metals in alcohols are the subject of numerous investigations because of the application of mentioned solvents in chemical engineering, production of oxide nanoparticles (sol-gel techniques) and application of alcohols as fuels. Despite relatively rich bibliography related to electro-catalytic oxidation of alcohols on metal surface in mixed aqueous–alcohol solutions, the knowledge of the mechanism of reactions on metal/anhydrous alcohol interface is still not sufficient. Anodic oxidation of metal surface in alcohol leads to several electro-catalytic reactions with formation of surface compounds being the product of metal and alcohol oxidation. Identification of these products is very difficult. Therefore, our knowledge of the composition and structure of passive films or corrosion products on metal surface in anhydrous alcohol solvents is poor. Our paper presents the investigations of anodic behaviour of metals (Cu, Zn, Fe, Ni, Al and Ti) and semiconductors (p-Si) in methanol solutions of electrolytes, performed in our laboratory within the last 10 years. On the base of electrochemical measurements (linear sweep voltammetry, electrochemical impedance spectroscopy), spectroscopic investigations (X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy and low-energy electron diffraction) and scanning electron microscopy techniques, the role of metal–alcohol intermediates in the formation of surface and soluble compounds is discussed. The practical application of electrochemical etching of metals as a method of production of micro- and nanoparticles of metals and oxides is also shown.     

中温NaCl-水蒸气协同作用下铁的腐蚀机理

应用电偶电流测试法研究在中温固态NaCl盐膜-水蒸气协同作用下,纯铁的腐蚀电化学反应机理.交流阻抗(EIS)法和SEM测试表明,阻抗谱能有效地表征材料表面氧化膜的存在以及反应过程氧化物的变化趋势,其中金属的氧化层电阻与腐蚀速率之间有较好的对应关系.     

An electrochemical impedance immunoanalytical method for detecting immunological interaction of human mammary tumor associated glycoprotein and its monoclonal antibody

An electrochemical impedance immunosensor has been developed for the specific detection of immunological interaction between human mammary tumor associated glycoprotein and its monoclonal antibody (GP1D8). Antibody proteins were immobilized by spontaneous adsorption of antibody on gold. Consequently, electrochemical impedance spectroscopy (EIS) measurements of a gold electrode coated with the antibody showed changes in a.c. current response after the addition of the specific antigen. The successful immunological reaction between the immobilized antibody–antigen at the electrode surface could be monitored.     

DNA‐Modified Screen‐Printed Electrodes with Nanostructured Films of Multiwall Carbon Nanotubes,Hydroxyapatite and Montmorillonite

Nanostructured films were deposited at the surface of working electrode of the screen‐printed assembly and utilized for the surface modification with double‐stranded DNA. The basic electrochemical properties of the sensors were investigated using voltammetric methods. Modified electrodes were also characterized by scanning electron microscopy and electrochemical impedance measurements. It was found that the electrode modification with DNA and nanomodifier leads to an enhanced sensitivity of the DNA voltammetric detection. New potentialities of the utilization of the K₃[Fe(CN)₆] cyclic voltammetric signal and electrochemical impedance spectroscopy were found. The DNA‐based biosensors showed good repeability and necessary stability within several days.     

Evaluation of passive film behaviour of super austenitic stainless steels at different potential regions using dynamic electrochemical impedance spectroscopy

Potentiodynamic anodic polarisation and dynamic electrochemical impedance spectroscopic (DEIS) measurements were carried out on 316L stainless steel and alloys 926 and 31 in natural seawater in order to assess the crevice corrosion resistance. DEIS measurements were performed over a wide range of potentials covering the corrosion potential, passive region, breakdown region and dissolution region. The impedance measurements in potentiodynamic conditions clearly reveal the changes that occur in the passive layer with change in potential. The impedance spectra at different potential regions were also discussed elaborately. The surface morphology of the alloy after crevice corrosion was studied using optical microscope and atomic force microscopy.     

肝素钠掺杂球状聚吡咯的合成及其电化学电容

以生物制剂肝素钠为掺杂剂,由自组装方法合成出平均粒径为100 nm的球状聚吡咯(PPy),用作超级电容器电极材料.透射电镜(TEM)、循环伏安、恒流充放电和电化学交流阻抗测试表明,肝素钠掺杂聚吡咯呈现较好的形貌和电容性质,在电流密度3 mA/cm2下充放电,单电极比电容达到338 F/g.     

The Electrochemical Investigation of MEH-PPV in Ionic Liquid

Ionic liquids are a new kind of room-temperature molten organic salts. It can be used as solvents in the organic/polymeric syntheses, and some of them are called "green" solvents because of its recyclability1. Ionic liquids possess the superior properties, such as thermal stability up to 200(C, involatility and re-designability(for both cation and anion). The ionic liquid employed in this work is [bmim] [PF6]- ( butylmethylimidazolium hexafluorophosphate ) which is immiscible with water and h…     

Preparation of Silver Nanoparticles‐Based Sensors for the Electrochemical Detection of Thiourea in Leaching Solutions of Waste Electrical and Electronic Equipment

Waste of electrical and electronic equipment is an interesting secondary resource of base and precious metals. Particularly the use of thiourea‐leaching in acidic medium was proposed for noble metals recovery. In this work, a novel and easy‐to‐use electrochemical sensor was developed, aimed to test thiourea from leaching solutions containing significant thiourea and copper amounts. The sensor was constructed using silver nanoparticles (AgNPs) deposited on screen‐printed electrodes. Its performance was studied in a synthetic leaching solution; changes in the overall surface charge of AgNPs resulting in changes in the charge‐transfer resistance for the copper ions were evaluated by electrochemical impedance spectroscopy.     

Revisiting the Electrochemical Impedance Spectroscopy of Magnesium with Online Inductively Coupled Plasma Atomic Emission Spectroscopy

The electrochemical impedance of reactive metals such as magnesium is often complicated by an obvious inductive loop with decreasing frequency of the AC polarising signal. The characterisation and ensuing explanation of this phenomenon has been lacking in the literature to date, being either ignored or speculated. Herein, we couple electrochemical impedance spectroscopy (EIS) with online atomic emission spectroelectrochemistry (AESEC) to simultaneously measure Mg‐ion concentration and electrochemical impedance spectra during Mg corrosion, in real time. It is revealed that Mg dissolution occurs via Mg²⁺, and that corrosion is activated, as measured by AC frequencies less than approximately 1 Hz approaching DC conditions. The result of this is a higher rate of Mg²⁺ dissolution, as the voltage excitation becomes slow enough to enable all Mg²⁺‐enabling processes to adjust in real time. The manifestation of this in EIS data is an inductive loop. The rationalisation of such EIS behaviour, as it relates to Mg, is revealed for the first time by using concurrent AESEC.     

硅片表面多金属污染的交流阻抗表征

在接近氢氟酸实际应用浓度条件下, 利用交流阻抗技术研究了硅片表面金属微观污染行为, 在氢氟酸溶液中分别加入0.5和1 mg/g的铜、铁、镍、钙四种金属离子, 获得了硅片在单金属溶液中的特征交流阻抗谱, 并在此基础上研究了三种金属及四种金属共存时的特征交流阻抗谱, 通过等效电路的拟合估算了硅/氢氟酸界面电化学反应的动力学参数, 并结合扫描电镜形貌图探讨了不同类型的单金属和多金属对硅电化学行为的影响. 结果表明, 多金属微观污染是各种单金属协同作用的结果, 铜在硅片上发生电化学沉积, 直接导致硅片表面粗糙化. 铁对硅片表面的破坏严重, 同时影响铜的沉积. 镍的存在使硅片表面更容易氧化. 而钙通过在硅片表面形成氟化钙沉淀物可以钝化表面, 减缓铜在硅片表面的沉积.     

Electrochemical study of ion transfer of acetylcholine across the interface of water and a lipid-modified 1,2-dichloroethane

The ion transfer of acetylcholine (AcH(+)) ions across the unmodified and phospholipid-modified water|1,2-dichloroethane (DCE) interface has been studied by means of square-wave and cyclic voltammetry, as well as by electrochemical impedance spectroscopy. After being transferred in the organic phase, the AcH(+) ions undergo chemical reactions with the phospholipids. The overall behavior of the experimental system studied in the presence of phospholipids has been compared with the theoretical results of an ECrev reaction. The kinetic parameters of the chemical interactions between AcH(+) and the phospholipids have been determined from the voltammetric and impedance measurements. Additional characterization of those interactions has been made by using the surface tension measurements.     

A study on the electrochemical polymerization, characterization, and corrosion protection of o-toluidine on steel

Poly(o-toluidine) (POT) coatings were electrochemically synthesized on 304 stainless steel using cyclic voltammetric method. These coatings were characterized by Fourier transform infrared spectroscopy, UV–vis absorption spectroscopy, and cyclic voltammetry. The corrosion performance of POT coating in aqueous 3 wt% sodium chloride was assessed by the electrochemical techniques such as open circuit potential measurements, potentiodynamic polarization technique, cyclic potentiodynamic polarization measurements, and electrochemical impedance spectroscopy. The results reveal that POT coating on 304 stainless steel prevents general and localized corrosion, and reduces the exchange current density almost by a factor of 45 than bare 304 stainless steel.     

Electrochemical characterization of a bioceramic material: The shell of the Eastern oyster Crassostrea virginica

The shell of the Eastern oyster (Crassostrea virginica) is composed of multiple incongruent mineralized layers. This bioceramic composite material was investigated to determine the effects of shell thickness, orientation and layer composition on its electrochemical behavior using electrochemical impedance spectroscopy, potentiodynamic polarization and scanning electron microscopy-energy dispersive spectroscopy. SEM-EDS analysis of the oyster shell revealed that the multilayered biocomposite material is composed of calcium carbonate (CaCO(3)). EIS measurements in 3.5wt.% NaCl indicated that the impedance of the whole oyster shell in the low frequency region exhibited high impedance values which exhibited a decreasing trend with increasing immersion time. In terms of overall shell thickness, limiting currents measured by potentiodynamic techniques through the shell were observed to increase when the outer layers of the shell were sequentially removed by grinding, thus decreasing the shell thickness. These limiting current values remained relatively constant when the inner layers of the shell were removed. The impedance values of the oyster shell material as measured by EIS were shown to decrease with decreasing shell thickness. These findings suggest that the prismatic (outermost) shell layer in combination with the soluble organic matrix between all shell layers may influence the ionic conductivity through the oyster shell.     

Investigation effect of benzotriazole on the corrosion of brass-MM55 alloy in artificial seawater by dynamic EIS

The electrochemical behavior of brass-MM55 alloy was studied in artificial seawater with benzotriazole by using a novel method called dynamic electrochemical impedance spectroscopy (DEIS). This method gives possibility to investigate the protection of metals in corrosive medium by using inhibitors in galvanostatic conditions for a long time. Instantaneous impedance spectra for brass-MM55 were recorded for 10 h in artificial seawater for different concentration of benzotriazole. It was found that a few hours were not enough for the accurate calculation of corrosion inhibition. Also with this method it is possible to figure out how the charge transfer resistance (R _ct) changes by the time. Usefulness of the DEIS technique in the investigation of non-stationary phenomena has been proved in the field of inhibitor research. All studies clearly show that benzotriazole inhibits the corrosion of brass-MM55 alloy in artificial seawater solution and the value of inhibition efficiency increases with increasing concentration of benzotriazole.     

Local electrochemical investigation of copper patina

The patination of copper is known for its complexity and heterogeneous formation. For a deeper investigation, a locally resolved surface analysis was considered. An exact determination of the accessed area and a potentiostatic control in a three-electrode configuration was reached with the use of the electrochemical microcell technique, which enables local electrochemical measurement such as local electrochemical impedance spectroscopy and cyclic voltammetry. Such a technique provides a unique way for performing the investigation of heterogeneities on electrode surfaces. The local electrochemical measurements on the artificially patinated surface have allowed distinguishing areas of different reactivity even when the analysis of the surface revealed a homogenous chemical composition of patina. Local measurements with the electrochemical microcell showed the presence of small defects on the patina layer that can be modelled by considering a hemispherical diffusion process at small active areas surrounded by larger less reactive domains.     

Argan hulls extract: green inhibitor of mild steel corrosion in 1?M HCl solution

Argan hulls extract (AHE) was tested as corrosion inhibitor for mild steel in 1?M HCl. Weight loss measurements, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) revealed that inhibiting action increased with increasing concentration of the inhibitor. The highest efficiency 97.3% was obtained at 5?g/L AHE. There was good agreement between gravimetric and electrochemical methods (potentiodynamic polarization and EIS). Results obtained from EIS measurements were analyzed to model the corrosion-inhibition process by use of the appropriate equivalent circuit model; a constant phase element was used. Polarization measurements show also that AHE acts as good mixed inhibitor. AHE is adsorbed on the steel surface in accordance with a Langmuir isotherm adsorption model.     

Electrochemical characterization of MWCNT/Ni(OH)<Subscript>2</Subscript> composites as cathode materials

The hydrothermal method was used to synthesize multi-walled carbon nanotube/nickel hydroxide composites (MWCNT/Ni(OH)₂). The structure and morphology of the prepared materials were characterized by X-ray diffraction and transmission electron microscopy. The electrochemical performance of cathodes prepared with multi-walled carbon nanotubes (MWCNT) loaded into the β-nickel hydroxide materials was investigated employing cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopic measurements. It is shown that the cathode active material utilization increases for MWCNT/Ni(OH)₂ obtained after 24 h of hydrothermal synthesis. These composites exhibit a fairly good electrochemical performance as cathode materials. Based on the results, this fact could be associated with the formation of a continuous conductive network structure in the hydroxide matrix. The analyses of impedance data, according to a physicochemical model, allow the improvement of a better understanding of the main structural and physicochemical parameters that control the electrochemical performance of these systems.