Impact of sensitization on dissolution process of AISI 304 stainless steel during intergranular corrosion evaluated using DEIS technique

The paper presents the results of instantaneous impedance changes measurements vs. reactivation potential performed by means of dynamic electrochemical impedance spectroscopy (DEIS) technique for AISI 304 stainless steel (SS) dissolution process during intergranular corrosion (IG) in 0.5 M H₂SO₄ + 0.01 M KSCN solution. With the use of DEIS method, it was possible to estimate dynamic changes of the examined system’s impedance in conditions of proceeding IG process. Furthermore, the paper proposes an alternative way of evaluating AISI 304 stainless steel dissolution rate during intergranular corrosion based on approximation to theory of iron dissolution in sulfuric acid medium. Simultaneously, based on the DEIS measurements, information about the degree of sensitization of the examined material were obtained. Performed research revealed the advantages of the DEIS technique over the classical double-loop electrochemical potentiokinetic reactivation tests when investigating intergranular corrosion process.     

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.     

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.     

不同晶粒度螺纹钢的电化学行为及其钝化膜的Mott-Schottky 研究

利用交流阻抗谱和极化曲线研究比较了四组不同晶粒尺寸的螺纹钢在模拟海水液(3.5% NaCl)中短期电化学腐蚀行为; 利用硼酸缓冲液中钝化膜的Mott-Schottky 理论比较了各试样在不同阳极极化电位下的钝化膜的优劣性. 结果表明, 在14 d 的模拟海水短期浸泡期间, 细晶粒螺纹钢在后期表现出较大阻抗值和较小的自腐蚀电流密度, 耐蚀性能优于粗晶粒试样. 在硼酸缓冲液中形成的钝化膜表现出典型的n 型半导体性能, 公共钝化区间为-0.15～0.8 V. 在选取的-0.1, 0.2, 0.5 V 三个不同极化电位下, 细晶粒螺纹钢在硼酸缓冲液中的钝化膜稳定性、耐蚀性弱于粗晶粒螺纹钢. 在0.5 V 的外加电压下试样钝化膜的内层膜消失, 钝化膜的施主浓度最低, 膜最为致密、稳定.     

Characterization of surface composition on Alloy 22 in neutral chloride solutions

The composition of anodically grown oxide films on Alloy 22, a Ni‐Cr‐Mo(W) alloy, has been investigated in 5 mol l^?1 NaCl at room temperature using X‐ray photoelectron spectroscopy and time‐of‐flight secondary ion mass spectrometry. For applied potentials up to 0.2 V (vs Ag/AgCl (saturated KCl solution)), a Cr(III) oxide barrier layer develops at the alloy/oxide interface accounting for the excellent passivity demonstrated to prevail in this potential region by previous electrochemical impedance spectroscopy measurements. At higher potentials, this layer is destroyed by defect injection as Cr(III) is oxidized to the more soluble Cr(VI). The overall oxide/hydroxide film thickness is, however, increased as Mo(VI)/W(VI) species accumulate at the oxide solution interface. The potential of 0.2 V at which the barrier layer switches from growth to destruction coincides with the previously demonstrated threshold potential for the initiation of crevice corrosion. Copyright © 2012 John Wiley & Sons, Ltd.     

碳钢缝隙内溶液化学和阳极极化行为研究

为研究缝隙腐蚀的溶液化学和缝中金属阳极极化行为,设计一种楔形缝隙模拟装置。以碳钢为研究对象,分别测试了在３．５％（ｗｔ）ＮａＣｌ溶液中缝内各位置的电极电位,Ｃｌ＾－浓度,ｐＨ值以及缝外阳极极化时电流密度的变化。     

Electrochemical behavior of CoCrMo implant in Ringer's solution

CoCrMo has been successfully employed as an orthopedic and orthodontic material because of its excellent corrosion resistant and suitable biocompatibility. The purpose of this research was to investigate the susceptibility of CoCrMo in Ringer's solution at three different temperatures: 22 °C, 37 °C, and 60 °C. The corrosion behavior of CoCrMo was carried out by using common electrochemical methods such as open circuit potential, potentiodynamic measurement, electrochemical impedance spectroscopy (EIS), and Mott–Schottky measurements. CoCrMo was passivated by the air, forming a passive film, which was not destroyed during the immersion in electrolytes under different temperatures. Results from potentiodynamic tests showed that at high anodic potentials, the passive film did not demonstrate significant localized corrosion and rather exhibited overall passive film degradation corresponding to the general corrosion of the alloy in Ringer's solution at the three temperatures. EIS measurements showed the presence of the stable passive film on the alloy surface when tested at open circuit potential. Mott–Schottky test indicated that the preformed passive film is an n‐type semiconductor due to the presence of a donor species. This is implied by the existence of oxygen vacancies and interstitial metallic cations. As the potential increased, the Cr³⁺ oxidized and produced soluble Cr⁴⁺ species. This resulted in the film changing to a p‐type semiconductor owing to the dissolution and creation of cation vacancies (acceptor species). The passive film rupture was not due to p‐type characteristics but rather was a result of the considerable oxidative dissolution of the film at high anodic potential. Copyright © 2013 John Wiley & Sons, Ltd.     

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.     

铬对碳钢在NaHCO3/NaCO3缓冲溶液中所成钝化膜半导体性能的影响

应用电化学阻抗谱技术研究铬对碳钢钝化膜半导体性能的影响.实验表明,在碳酸氢钠/碳酸钠缓冲溶液中碳钢形成的钝化膜具n型半导体特性,而含有3%铬的碳钢钝化膜则呈n-p型半导体特性,随着成膜电位的增加,以上两种钝化膜之Mott-Schottky直线部分的斜率均呈增大的趋势,表明成膜电位升高,膜内的杂质密度减小,但铬的加入使得碳钢钝化膜的施主密度增加约一个数量级,从而增加了碳钢点蚀发生的趋势.EIS分析表明:铬的加入降低了钝化膜的传递电阻R1和膜电阻R2,特别是膜电阻R2下降达3个数量级,这就有可能增加碳钢在高pH值环境中的腐蚀.     

Characterization of the passive films on electrodeposited Fe-Ni-Cr alloys in borate solution at pH 8.4

The corrosion properties of the passive layers formed on iron-nickel-chromium electrodeposits of Fe₂₉Ni₅₁Cr₂₀ were investigated in 0.3 M borate solution at a‘ pH of 8.4. On the basis of measurements by cyclic voltammetry, chronopotentiometry and electrochemical impedance spectroscopy, a low passive dissolution/corrosion rate was identified for the electrodeposited Fe-Ni-Cr alloys due to the nature of the established corrosion layer. The stability of this passive layer was further enhanced after corrosion under oxidizing conditions. Mössbauer spectroscopic measurements confirmed the existence of a thin passive layer on the amorphous electrodeposits.      

An Impedance Molecularly Imprinted Sensor for the Detection of Bovine Serum Albumin (BSA) Using the Dynamic Electrochemical Impedance Spectroscopy

A molecularly imprinted electrochemical sensor is successfully developed to detect bovine serum albumin (BSA) based on the dynamic electrochemical impedance spectroscopy (DEIS) instead of the traditional impedance spectroscopy. The sensor is prepared using chitosan and pyrrole as modified material and functional monomers, respectively, and the fast and real‐time characterization of molecular imprinting process can be obtained by DEIS. It is indicated that the removal and rebinding processes of BSA are closely related with the DEIS impedance under dynamic conditions, and the direct correlation between the resulting kinetic information and BSA concentrations can be established. As a result, the impedance changing rates in the initial 5 min of BSA adsorption are linear to the BSA concentrations ranging from 0.0001 to 0.01 ng mL^?1 and 0.01 to 1 ng mL^?1 with a detection limit of 5×10^?5 ng mL^?1 (S/N=3). In addition, the detection of BSA by DEIS does not require the system to be in equilibrium. The sensor also shows simplicity, high sensitivity, good stability and acceptable recovery in real samples, indicating its promising prospects in the fast and real‐time detection of proteins.     

Surface characterisation and crevice corrosion behaviour of nickel-based alloys in the paper industry

Recycled water in the paper industry acts as a stronger electrolyte as its concentration and temperature are quite high. The lower pH that exists in these solutions enhances the corrosion and the high concentration of solids leads to leaching of metal ions from surface. Crevice corrosion is a form of localised attack, which can quickly induce metal perforation even with high grade stainless steels like 316L when the protective chromium oxide film is damaged. A specially designed crevice cell assembly was used to study the electrochemical aspects of nickel-based alloys with the commonly used 316L SS. The mounted specimen with its crevice was anodically polarised in a white water medium, which is normally encountered in the paper machine section. The nickel-based alloys show remarkable crevice corrosion resistance. X-ray photoelectron spectroscopy studies revealed that the enhanced corrosion resistance of these alloys is due to the contributing nature of the individual elements Cr, Ni and Mo and their presence in the form of various oxidised species on the passive films. Received: 22 February 1999 / Accepted: 6 June 1999     

不锈钢钝化膜耐蚀性与半导体特性的关联研究

通过极化曲线、交流阻抗谱和钝化膜半导体特性等电化学测量，研究了经电化学阳极氧化处理的不锈钢钝化膜在0.5 mol•L^-1 NaCl溶液中耐蚀性能与其半导体特性的关系，进一步探索电化学改性处理不锈钢钝化膜的耐蚀机理. 结果表明，不锈钢钝化膜在负于平带电位范围表现为p型半导体，在高于平带电位范围表现为n型半导体，这主要与组成钝化膜的Fe和Cr氧化物半导体性质有关. 与自然条件下形成的不锈钢钝化膜比较，发现经过电化学阳极氧化后不锈钢钝化膜具有较低的施主与受主浓度，平带电位负移，说明阴离子在钝化膜表面发生吸附. 低的施主与受主浓度及钝化膜表面负电荷的增强，可有效排斥侵蚀性Cl^－在钝化膜表面的特性吸附，有利于提高不锈钢的耐局部腐蚀性能.     

饱和NaCl溶液浸泡下混凝土试块中有机阻锈剂对钢筋腐蚀行为的影响

利用电化学阻抗谱(EIS)、半电池腐蚀电位(Ecorr)和宏观电池腐蚀电流密度(Icorr)测量技术,在饱和NaCl溶液浸泡的硬化混凝土试块中,研究了4种醇胺基阻锈剂对钢筋电极腐蚀电化学行为的影响和长期阻锈性能.在浸泡初始的100d内,与空白样相比,添加阻锈剂后钢筋电极腐蚀电位升高,阻抗膜值增大,腐蚀电流密度值降低,表明电极表面处于钝态,阻锈剂表现出良好的阻锈性能.随浸泡时间延长,电极腐蚀电位和阻抗膜值下降,腐蚀电流密度增大.浸泡后期,除添加醇胺基CI-4样外,电极电位和腐蚀电流密度与空白样相比无明显差别,表明电极由钝态转变为活性腐蚀状态.但添加CI-4样品,钢筋电极始终保持在钝化状态,阻锈性能最好.基于阻锈剂与Cl-间的竞争吸附,分析探讨了可能的阻锈机理.     

Electrochemical studies for the electroactivity of amine-capped aniline trimer on the anticorrosion effect of as-prepared polyimide coatings

The electroactive polyimide consisting of various content of amine-capped aniline trimers (ATs) have been successfully synthesized and characterized by Fourier-Transformation infrared and UV-visible absorption spectroscopy. The electroactivity of as-prepared polyimides was tested by electrochemical cyclic voltammetry (CV) studies. It was noticed that the as-prepared electroactive polyimide with higher content of amine-capped ATs shows higher electroactivity (i.e., larger redox current) than that of non-electroactive polyimide, leading to enhance corrosion protection efficiency on cold-rolled steel (CRS) electrodes. This enhanced corrosion protection efficiency has been explained based on a series of electrochemical measurements such as corrosion potential, polarization resistance, corrosion current and electrochemical impedance spectroscopy (EIS) studies in 5 wt-% NaCl electrolyte. This significant enhancement of corrosion protection on CRS electrodes as compared to non-electroactive polyimide might probably be attributed to the redox catalytic property of as-prepared electroactive polyimide coatings inducing the formation of passive layer of metal oxide.     

Dynamic electrochemical impedance spectroscopy measurements of passive layer cracking under static tensile stresses

Electrochemical impedance spectroscopy allows the examination of corrosion susceptibility and resistance for different construction materials, in particular the determination of the properties of their passive films. This technique makes possible the analysis of electrochemical processes in time domain, including rapid phenomena such as changes in the properties of passive films, but it has never been used for passive layer cracking examination. In many cases, fracture of the passive film under tensile stresses leads to stress corrosion cracking. Therefore, investigations of passive layer cracking on austenitic stainless steels under tensile stresses facilitate the understanding of the mechanism of stress corrosion cracking in these common engineering materials. The effect of static tensile stresses on the passive film cracking behaviour of type 304L stainless steel immersed in 0.5 M NaCl solution at room temperature has been investigated. This paper presents the impedance spectra obtained for 304L stainless steel samples at different potential values.Contribution to the 3rd Baltic Conference on Electrochemistry, Gdansk-Sobieszewo, Poland, 23–26 April 2003Dedicated to the memory of Harry B. Mark, Jr. (28 February 1934–3 March 2003)     

Numerical Simulation for Crevice Corrosion of 304 Stainless Steel in Sodium Chloride Solution

The authors presented a mechanistic model describing the chemical reactions within a corroded thin, nar-row crevice. In the mathematical model, a two-dimensional steady-state was used to predict the crevice pH profile by taking into account dissolved oxygen and hydrogen ions within the crevice. It consists of six parallel electrochemical reactions: multi anodic reactions(Fe, Cr, Ni dissolution reactions) and three cathodic reactions(the oxygen reduction, the hydrogen reaction and water dissociation). Current density distribution and oxygen concentration distribution were determined to be corresponding to the evolution of potential distribution within the crevice. The contribution of each metal reaction to the overall corrosion process was in proportion to the mole fraction, and the simulation pro-vided a good agreement with published experimental results for the crevice corrosion of stainless steel in sodium chloride solution.     

690合金在300 ℃含硫模拟碱性水化学中的腐蚀行为

690 合金作为压水堆核电站蒸汽发生器传热管的一种关键材料, 其在碱性环境下还原态硫导致的钝化膜的腐蚀退化是引发应力腐蚀开裂的关键原因之一. 本文采用动电位极化曲线, 结合扫描电镜(SEM)、俄歇能谱(AES)、二次离子飞行时间质谱(ToF-SIMS)研究了690合金在300 ℃模拟碱性水化学中的腐蚀行为, 并分析了硫代硫酸根与硫酸根对钝化膜特性的影响. 实验结果表明: 300 ℃碱性溶液中690合金表面钝化膜为外层的多孔层与内层的紧密层组成的双层结构, 所加入的硫酸盐种类对690合金的耐蚀性有较大影响; 硫代硫酸根使690合金钝化电流密度增加, 过钝化电位降低, 即钝化膜的耐蚀性降低; 此外, 硫代硫酸根使钝化膜中的Cr含量降低而Ni 含量提高, 硫代硫酸根会在合金表面电化学还原成为更低价态的硫进入钝化膜, 使钝化膜中的硫化物增多也是导致钝化膜防护性能变差的原因; 而硫酸根与钝化膜的作用较弱, 对钝化膜的影响较小.     

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.