Online Monitoring of the Atmospheric Corrosion of Aluminium Alloys Using Electrochemical Noise Technique

In this work, an electrochemical system based on electrochemical noise (EN) technique for online detection and monitoring of atmospheric corrosion of LY12CZ aluminium alloys has been established. A detecting probe and a monitoring instrument with a software have been developed to perform the electrochemical noise measurements with zero resistance ammeter (ZRA) mode. Experimental results show that the atmospheric corrosion behaviour of aluminium could be effectively detected and monitored by the analysis of the electrochemical potential and current noise, also by the noise resistance variation.     

Electrochemical noise diagnostics of PEM fuel cell stack for micro-cogeneration application

Journal of Solid State Electrochemistry - Electrochemical noise (EN) generated by a 3500 W PEM fuel cell stack (50 cells) has been measured during micro-cogeneration durability tests. The...     

干湿循环下混凝土中钢筋腐蚀的电化学检测

应用电化学噪声技术,结合电化学阻抗谱研究了干湿循环条件下3种不同pH值的3.5%NaCl溶液中混凝土钢筋的腐蚀过程.结果表明,钢筋的腐蚀分为3个阶段:钝化膜的溶解期、腐蚀活化期和腐蚀产物的累积期.在pH1的溶液中经过30个干湿循环后主要以均匀腐蚀为主,而对pH3和pH7溶液,则主要以点蚀为主,散粒噪声分析证实了混凝土中钢筋在强酸性溶液中更容易发生腐蚀.电化学阻抗谱分析也进一步说明了混凝土中钢筋的腐蚀经历了3个阶段:第1阶段Nyquist谱图中出现两个时间常数,高频区为混凝土层的容抗性质,低频区为钢筋与混凝土界面的电荷转移电阻;第2阶段,中频区增加一个时间常数,这与腐蚀产物的累积有关;第3阶段,随着腐蚀产物向混凝土中的扩散,中频区容抗弧有所减小,特别是pH1体系,中频弧几乎消失.SEM形貌表征观察到随着溶液酸度的增加钢筋表面的锈层明显增多.     

Catalysis in high-temperature fuel cells

Catalysis plays a critical role in solid oxide fuel cell systems. The electrochemical reactions within the cell--oxygen dissociation on the cathode and electrochemical fuel combustion on the anode--are catalytic reactions. The fuels used in high-temperature fuel cells, for example, natural gas, propane, or liquid hydrocarbons, need to be preprocessed to a form suitable for conversion on the anode-sulfur removal and pre-reforming. The unconverted fuel (economic fuel utilization around 85%) is commonly combusted using a catalytic burner. Ceramic Fuel Cells Ltd. has developed anodes that in addition to having electrochemical activity also are reactive for internal steam reforming of methane. This can simplify fuel preprocessing, but its main advantage is thermal management of the fuel cell stack by endothermic heat removal. Using this approach, the objective of fuel preprocessing is to produce a methane-rich fuel stream but with all higher hydrocarbons removed. Sulfur removal can be achieved by absorption or hydro-desulfurization (HDS). Depending on the system configuration, hydrogen is also required for start-up and shutdown. Reactor operating parameters are strongly tied to fuel cell operational regimes, thus often limiting optimization of the catalytic reactors. In this paper we discuss operation of an authothermal reforming reactor for hydrogen generation for HDS and start-up/shutdown, and development of a pre-reformer for converting propane to a methane-rich fuel stream.     

Electrochemical Noise Measurement of Polymer Membrane Fuel Cell under Load

Electrochemical noise of a polymer membrane hydrogen–air fuel cell under different currents is measured. Frequency and amplitude dependences of the current-noise power spectral density are calculated. In the frequency interval from 10 to 200 Hz a linear segment of the frequency characteristic has a slope of ?2. The current-noise power spectral density is found to be proportional to the 4th power of the fuel cell loading DC current. Thus found frequency dependence of the fuel cell electrochemical noise was shown to differ markedly from that of the electrochemical impedance real component.     

Corrosion-wear monitoring of TiN coated ASP23 steel by electrochemical noise measurements

A modified electrochemical noise (EN) technique has been applied to monitor corrosion-wear of TiN coated ASP23 steel sliding against corundum in 0.5 M H₂SO₄. Experimental results show that corrosion-wear mechanisms of TiN coatings depend on their substrate properties. When the substrate is active, such as ASP23 tool steel, the electrochemical noise is dominated by dissolution of the substrate at the pinholes and the hydrogen evolution all over the exposed surface.     

腐蚀金属电极的电化学频域测量研究进展──金属腐蚀与防护研究所电化学研究介绍之一

腐蚀金属电极的电化学频域测量研究进展──金属腐蚀与防护研究所电化学研究介绍之一曹楚南（金属腐蚀与防护国家重点实验室,金属腐蚀与防护研究所,沈阳１１００１５）腐蚀电化学是研究与腐蚀有关的电化学问题,具体的研究对象为腐蚀金属电极。虽然电化学中的基本原理和...     

Analysis of electrochemical noise by means of bispectral technique

Nonlinear processes are often encountered in the practice of electrochemical and corrosion measurements. Especially, activation-controlled processes are inherently nonlinear. Taking into account investigations of electrode reactions, linear approximation is a popular approach. In this introductory paper, the possibility of extension of electrochemical noise (EN) measurements to the nonlinear regime is presented. Natural consequence of focusing on nonlinear processes is application of higher-order spectral techniques. Utilization of bispectral representation enables analysis of stationarity and linearity properties of EN. The authors present algorithm enabling assessment of both quantities and also exemplary analysis of noise generated during cathodic polarization, which is important for corrosion protection. Presented at the 4th Baltic Conference on Electrochemistry, Greifswald, 13–16 March 2005. Presented at the 4th Baltic Conference on Electrochemistry, Greifswald, March 13–16, 2005.     

Coherent Resonance for Rate Oscillations During CO Oxidation on Pt(110) Surfaces: Interplay Between Internal and External Noise

Effects of noise on rate oscillations during CO oxidation on Pt(110) surface were investigated, both theo-retically and numerically, by focusing on the interplay of internal noise (IN) due to stochasticity in reaction events, and external noise (EN) resulting from parameter perturbation. The surface is divided into cells of variable size which are assumed to be well mixed, and we consider the behavior inside a single cell. At-tention is paid to parameter regions subthreshold of the deterministic Hopf bifurcation, where noise can induce stochastic oscillations, the signal-to-noise ratio (SNR) of which shows a maximum with the variation of noise intensity, known as coherent resonance (CR). By stochastic normal theory, we show that IN and EN contribute in a weighted additive way to an effective noise that lead to CR, such that SNR shows a ridge shape in the D-1/N plane, where D and 1/N measures the strength of EN and IN, respectively. It is shown that for too large IN (EN), CR behavior with EN (IN) no longer exists. Numerical simulations show good agreements with the theoretical results     

Q235碳钢缝隙腐蚀的电化学噪声研究

应用电化学噪声和电化学阻抗技术研究Q235碳钢在NaHCO3+NaCl溶液中的缝隙腐蚀行为.结果显示,缝隙腐蚀过程可以被清楚地划分为3个阶段:孕育期、快速转换期和稳定发展期.电化学噪声的特征和噪声电阻在各阶段有着显著的变化.缝隙外、内表面积比(r)对缝隙腐蚀的孕育和发展有着十分重要的影响:r越大,孕育期越长.但是,在缝隙腐蚀稳定发展期,r较小时,缝隙外电极表面处于活性溶解状态,缝隙内外电位差很小,缝隙内腐蚀速率较小;倘如r很大时,则缝隙外电极表面处于钝态,缝隙内外电位差大,最终将导致严重的缝隙腐蚀.     

Wavelet transform-based analysis for electrochemical noise

Wavelet transforms are presented as a useful tool to analyse electrochemical noise data. Various concepts developed in the framework of wavelet transforms have been adapted to study electrochemical noise measurements. The most relevant feature of this method of analysis is its capability of decomposing electrochemical noise records into different sets of wavelet coefficients, which contain information about corrosion events occurring at a determined time-scale. Thus, this mathematical approach could become an alternative tool which solves the limitations of other more established procedures for the analysis of electrochemical noise data, such as statistical or Fourier transform-based methods.     

Experimental correlation between metallographic evaluation and electrochemical noise in intergranular corrosion tests of aluminium alloys

In the present work, the correlation between the metallographic evaluation and electrochemical noise (EN) in intergranular corrosion (IGC) tests of aluminium alloy 2024‐T3 has been analysed. For this purpose, the influence of temperature and hydrogen peroxide concentration on the IGC attack has been studied. Similar IGC was observed between 20 and 40 °C, showing a low dependence with temperature (at least in this range). Hydrogen peroxide was seen to have a strong effect, leading to IGC activation when raising its concentration. The results of the detailed metallographic evaluation of the samples after the tests were analysed together with the EN measured during the tests. The averaged noise resistance was inversely proportional to the depths of the attacks, whereas the average of the parameter so‐called ‘Statistical Noise Power’ was directly related to the IGC degree. The metallographic evaluation and the EN showed a reasonable experimental correlation. Copyright © 2012 John Wiley & Sons, Ltd.     

A novel electrochemical noise sensor applied to detect food safety

A novel electrochemical noise (EN) sensor was elaborately designed to detect the metal residue in energy drinks. By calculating the characteristic parameter, noise resistance R _n, obtained from the EN data, the tin and iron residue can be semiquantitatively evaluated. In addition, R _n was further compared with the inductively coupled plasma mass spectrometer (ICP-MS) results. Accordingly, an interesting relationship was found between the EN data and ICP-MS results. The experimental results reveal that R _n can indirectly reflect the corrosion-induced metal release from the packaging materials; a lower R _n means a higher metal release. This electrochemical sensor has potential applications in evaluating food safety because of its fast, economic and in-situ features.     

Sensitive and Low-background Electrochemical Immunosensor Employing Glucose Dehydrogenase and 1,10-Phenanthroline-5,6-dione

We report a sensitive electrochemical immunosensor with a low electrochemical background level, which results from electrochemical-enzymatic (EN) redox cycling based on mediated electrochemical oxidation of an electro-inactive reductant (glucose) at 0.0 V. The EN redox cycling employs flavin adenine dinucleotide-dependent glucose dehydrogenase and 1,10-phenanthroline-5,6-dione (PD). When PD was compared with five common quinone-based electron mediators, PD enabled the highest signal-to-background ratio, due to a very low electrochemical background level. When EN redox cycling was applied to a sandwich-type immunosensor, parathyroid hormone (PTH) in serum could be detected with a very low detection limit of ∼0.1 pg/mL.     

Corrosion monitoring using electrochemical noise and linear polarization resistance in fuel oil combustion gas environment

Corrosion monitoring of different steels is carried out online in a combustion rig firing 32 kg/h of fuel oil. Two temperature-controlled probes are designed to allow control of the specimens temperature and the use of electrochemical noise (EN) and linear polarization resistance (LPR) techniques for corrosion monitoring. Two probes are placed where the combustion gas reached a temperature of 850–900°C, and another one at the combustion gas exit where the rig was at 200–240°C. Corrosion rates of an austenitic and a ferritic steel are obtained where the temperature of the combustion gas is 850–900°C, firing fuel oils with different content of Na-V-S. Corrosion monitoring of mild steel is carried out in the test burning a fuel oil with the higher content of Na-V-S by placing a corrosion probe in the low combustion gas temperature zone. The EN results show that this technique is able to assess the corrosion rate in an environment at high temperature where fuel oil ashes deposited and at a temperature high enough where they start to melt and a corrosion process proceeds. Results show that this technique is able to assess the corrosivity of fuel oil ashes originated from fuel oil containing different amounts of sodium, vanadium, and sulfur as corrosion causing impurities. Results of the low-temperature probe show that EN and LPR are able to detect the onset of corrosion on mild steel as a result of sulfuric acid condensation on the probe. However, the corrosion rates are not the same, because localized corrosion is taking place as detected by the EN technique. It is demonstrated that the use of two techniques for corrosion monitoring can give a better understanding of the corrosion process. Electrochemical techniques used to assess the corrosion resistance of alloys at high and low temperatures prove to be a valuable tool for the purposes of materials selection or controlling the main process variables that affect the corrosion resistance of materials in industrial equipment. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 5, pp. 627–632. The text was submitted by the authors in English.     

Iodinated carbon materials for oxygen reduction reaction in proton exchange membrane fuel cell. Scalable synthesis and electrochemical performances

Doped graphene-based cathode catalysts are considered as promising competitors for ORR, but their power density has been low compared to Pt-based cathodes, mainly due to poor mass-transport properties. A new electrocatalyst for PEMFCs, an iodine doped grahene was prepared, characterized, and tested and the results are presented in this paper. We report a hybrid derived electrocatalyst with increased electrochemical active area and enhanced mass-transport properties. The electrochemical performances of several configurations were tested and compared with a typical Pt/C cathode configuration. As a standalone catalyst, the iodine doped graphene gives a performance with 60% lower than if it is placed between gas diffusion layer and catalyst layer. If it is included as microporous layer, the electrochemical performances of the fuel cell are with 15% bigger in terms of power density than the typical fuel cell with the same Pt/C loading, proving the beneficial effect of the iodine doped graphene for the fuel cell in the ohmic and mass transfer region. Moreover, the hybrid cathode manufactured by commercial Pt/C together with the material with best proprieties, is tested in a H₂-Air fuel cell and a power density of 0.55 W cm⁻² at 0.52 V was obtained, which is superior to that of a commercial Pt-based cathode tested under identical conditions (0.46 W cm⁻²).     

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.     

Deactivation resistant PdSb/C catalysts for direct formic acid fuel cells

Formic acid oxidation at novel carbon supported PdSb alloy catalysts has been studied in a multi-anode direct formic acid fuel cell with supporting mechanistic studies in a conventional electrochemical cell. The optimized PdSb/C catalysts show better high voltage and long term performances than a comparable commercial Pd/C catalyst and much better resistance to poisoning (deactivation). Electrochemical stripping voltammograms show that the presence of Sb lowers the potential required for CO oxidation, and greatly decreases the accumulation of CO on the catalyst surface during formic acid oxidation.