Heterogeneous electrochemical characteristics of biofilm/metal interface and local electrochemical techniques used for this purpose

Biofilms on metal surface in an aqueous environment is a complex electrochemical system. The heterogeneous electrochemical characteristics of biofilm/metal interface and local electrochemical techniques used for this purpose are discussed in this work. The techniques presented in this work include microelectrode, scanning vibrating electrode, the wire beam electrode method, and scanning electrochemical microscopy. Two potentially useful techniques, localized electrochemical impedance spectroscopy and scanning Kelvin probe force microscopy, are also discussed. The advantages and limitations of these techniques are summarized. A new approach: numerical simulation of micro‐electrochemical heterogeneity of biofilm covered metals is introduced.     

LiNi_(0.5)Mn_(0.5)O_2电极在LiNO_3电解液中的电化学性能及循环衰减机理(英文)

研究LiNi0.5Mn0.5O2电极在LiNO3水溶液中的电化学行为,同时分析该电极在不同pH值电解液中的循环衰减原因。循环伏安测试显示LiNi0.5Mn0.5O2在浓度为5 mol/L的LiNO3水溶液中具有较好的锂离子脱嵌能力。对比发现,LiNi0.5Mn0.5O2电极在浓度为5 mol/L,pH值为12的LiNO3水溶液中具有最好的循环稳定性能。通过交流阻抗法、X射线衍射分析及电极形貌的对比分析发现:电极在浓度为5 mol/L,pH值为12的LiNO3水溶液中循环时,电极的表面形貌和电极结构都能得到较好的保持,电极的电荷传递阻抗得到明显抑制,因此在该pH值电解液中的循环稳定性最好。     

A study of the corrosion behavior of gamma titanium aluminide in 3.5 wt% NaCl solution and seawater

Gamma titanium aluminide (γ-TiAl) was evaluated for corrosion resistance in 3.5% NaCl and seawater using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Polarization plots indicate very low corrosion rates although in both electrolytes the control samples lost passivity at low polarization potentials. Surface modification treatments were employed by oxidizing the samples in air at 500 °C and 800 °C with the purpose of improving corrosion resistance. While the surface treatments rendered γ-TiAl passive in the polarization experiments in both electrolytes, EIS tests showed that the oxide formed at 800 °C was not protective. EEC models are proposed to explain the EIS results for the three surface conditions tested.     

The role of mass transfer in the formation of the composition and structure of CoW coatings electrodeposited from citrate solutions

The effect of the hydrodynamic conditions on the electrode process’s rate and the composition and structure of cobalt-tungsten coatings electrodeposited from citrate solutions is studied. The rate of the electrode process depends on the hydrodynamic conditions. However, the electrochemical impedance data do not reveal the presence of slow diffusion processes. The analysis of the electrochemical impedance spectra shows the occurrence of slow adsorption processes, such as an intermediate adsorption stage. It is assumed that the hydrodynamic conditions have a strong effect on the surface state rather than on the mass transfer from the solution’s bulk to the electrode.     

磷化处理对无铬钝化热镀锌板耐蚀性能的影响

研究了磷化处理工艺对无铬钝化热镀锌板耐腐蚀性能和表面形貌的影响。采用扫描电镜对其表面形貌进行分析，同时与未经过磷化处理的钝化板表面形貌进行对比；采用电化学阳极极化曲线方法和电化学阻抗法对磷化处理后钝化板的耐腐蚀性能进行了研究。在钝化板膜重为0.8 g/m²的情况下，经磷化处理的钝化板表面钝化膜完好，没有发现锈蚀或钝化膜剥落现象；经磷化处理的钝化板自腐蚀电位和阳极电流密度不变，阴极电流密度和自腐蚀电流密度有所提高；Nyquist图的高频部分在磷化处理前为容抗弧，磷化处理后出现具有Warburg阻抗的直线，说明磷化处理后钝化膜表面出现扩散过程。 研究表明，钝化板经过磷化处理后表面未形成磷化膜，耐腐蚀性能仍来自原钝化膜，经磷化处理的钝化板的耐腐蚀性能有所降低。因此，现有常规的磷化处理并没有增加钝化板的耐腐蚀性能，如果有需要提高钝化板耐腐蚀性能的要求，必须针对无铬钝化板研制专用的磷化液和磷化工艺。     

Composition and processing effects on the electrochemical characteristics of biomedical titanium alloys

The electrochemical behaviour of the Ti–13Nb–13Zr and Ti–6Al–4V ELI alloys with martensitic microstructures was investigated by polarization and electrochemical impedance spectroscopy (EIS) in Ringer’s solution. The impedance spectra were interpreted by a two time-constants equivalent circuit. Both investigated alloys showed high corrosion resistance, but the thin and uniform passive film on the Ti–6Al–4V ELI alloy surface was more protective. The inner barrier and outer porous layer were highly resistant and capacitive. However, thicker and more porous passive film on the Ti–13Nb–13Zr alloy surface may be beneficial for osteointegration. The suitable thermomechanical processing improved the corrosion resistance of Ti–13Nb–13Zr alloy.     

Study of the electrochemical properties of a transition metallic ions modified electrode in acidic VOSO4 solution

Graphite material was used as the electrode for an all-vanadium redox flow battery, and the electrode was modified by transition metallic ions to enhance its electrochemical behavior. An porous graphite composite electrode has high specific surface area and high current density. The electrode modified by transition metallic ions has improved catalysis behavior that can catalyze the V（Ⅱ）-V（Ⅴ） redox reaction showed by cyclic voltammograms. This article studied the impedance of the modified electrode by electrochemical impedance spectroscopy （EIS）, and approved that the electrode modified by Co^2＋ and Mn^2＋ has a lower charge transfer resistance than the non-modified electrode. The effect of average particle size distribution is at lower frequencies that the slope of Warburg impedance is reduced by large particle size distribution. The voltage efficiency of the Co^2＋ modified electrode test cell is 81.5%, which is higher than that of the non-modified electrode.     

AZ31镁合金在化学镀镀液中的电化学行为研究

采用混合电位-时间曲线、极化曲线和电化学阻抗谱,研究经不同浓度氢氟酸活化处理后的AZ31变形镁合金在化学镀镀液中的电化学行为,并通过扫描电子显微镜(SEM)观察AZ31活化前后的形貌变化.结果表明,经活化的试样在化学镀过程中被镀层完全覆盖,所用时间随着氢氟酸浓度的增加而延长;镀液中的镍离子被还原的起始电位随着氢氟酸浓度的增加而向正偏移;电极/镀液界面反应的电荷转移电阻随着氢氟酸浓度的增加而增大,并且电极/镀液界面反应是化学镀初始沉积期的控制步骤;AZ31镁合金基体中的Mn-Al相在氢氟酸活化过程中的颗粒脱落是导致氟化膜产生缺陷的主要原因,氢氟酸浓度越高,氟化膜缺陷越少.     

Electrochemical noise analysis: detection of electrode asymmetry

One major application of electrochemical noise (EN) analysis for corrosion studies is the estimation of corrosion rate via impedance measurement. The measurement involves coupling two electrodes, whereupon the associated EN is measured and the noise resistance and the spectral noise impedance are computed. However, the two electrodes are required to be “nominally identical” (i.e. symmetrical) for the noise resistance and spectral impedance techniques to be valid. This paper proposes that the correlation between the measured potential and the current noise can be used to detect an asymmetric electrode pair and thus provides a necessary but not sufficient test for electrode symmetry. The potential/current coefficient of correlation is derived based on an equivalent circuit to demonstrate the concept and experimental data is presented to support the theory.     

Electrochemical and XPS studies and the potential scan rate dependent pitting corrosion behavior of Zircaloy-2 in 5% NaCl solution

Electrochemical studies of Zircaloy-2 in 5% NaCl solution were carried out using polarization and electrochemical impedance spectroscopy (EIS). Scan rate dependent pitting behavior of Zircaloy-2 was observed when polarization experiments were carried out at different scan rates (5 mV/min, 50 mV/min and 500 mV/min). Polarization resistance, double layer capacitance, and the thickness of passive film were calculated from the EIS study. The slope of the Bode plot in the capacitive region showed non-ideal behaviour, suggesting formation of pits. A distribution of chloride concentration was seen at the surface of the electrode when the test solution was sampled from different parts of the sample surface and analyzed for chloride. Inclusion of chloride ions in the passive film was observed from the XPS study and the chloride concentration increases with the higher anodic polarization. The outermost layer of the passive film was rich in hydroxide and oxy-hydroxide. A bi-layer passive film structure on the alloy surface is proposed.     

腐蚀缝隙内电化学行为的初步理论探讨——1.腐蚀缝隙内电化学行为的数学模型

本文对腐蚀缝隙内的电化学行为进行了初步的数学解析。认为影响腐蚀缝隙内电化学行为的主要因素有:极化电场、缝隙形状、缝内表面状态、电化学反应,溶液性质和外加应力等,并将这些因素用等效电路的一系列参数来描述,即:极化电场用极化电位和电流来描述;电化学反应用等效反应电阻来描;溶液性质的差别用比电阻的变化来描述:表面状态和应力用表面等效阻抗来描述。由此得到几神情况下的微分方程及其解析解,对适合一般情况的微分方程进行了数值计算,计算值和测试结果比较一致。运用本文的数学模型,通过测试缝外电位,就可估算缝内任一点的电位。     

Effect of heat treatment on corrosion properties of CuAlNi shape memory alloy

The effect of heat treatment on corrosion properties of CuAlNi shape memory alloy was investigated in 0.9% NaCl solution at pH 7.4 and 37 °C by open circuit potential measurements, polarisation techniques, and electrochemical impedance spectroscopy. Investigations were performed on CuAlNi alloy samples in as-cast state and after heat treatment procedure containing annealing at 850, 885 and 920 °C followed by water quenching. Electrochemical impedance measurement results indicate that heat treatment of CuAlNi alloy leads to the increase in charge transfer resistance and surface layer resistance and the decrease in values of capacitance of the double and surface layers, indicating higher corrosion resistance compared with the as-cast CuAlNi alloy. The increase in polarisation resistance and the decrease in corrosion current density of heat-treated CuAlNi alloy also suggest beneficial influence of heat treatment on corrosion resistance of CuAlNi alloy. Optical microscopy, SEM/EDX and XRD analysis of samples surface after polarisation measurements show the occurrence of pitting corrosion on the electrode surfaces, with the existence of CuCl₂, AlCl₃ and Cu₂Cl(OH)₃ compounds as the surface corrosion products.     

5083铝合金搅拌摩擦焊接头微弧氧化膜电化学腐蚀行为

利用微弧氧化技术在5083铝合金搅拌摩擦焊(FSW)接头表面制备一层均匀的微弧氧化膜.通过动电位极化和电化学阻抗谱(EIS)分析,评估微弧氧化前后搅拌摩擦焊接头的腐蚀特性.结果表明,经过微弧氧化表面处理的搅拌摩擦焊样品腐蚀电流密度减小,电化学阻抗增加,抗腐蚀性能得到了显著改善.未氧化处理的不同焊接组织区域腐蚀行为存在明显的差异,而5083铝合金母相和焊缝表面的微弧氧化膜具有相同的形貌和抗腐蚀性能.     

Cathodic protection of XL 52 steel under the influence of sulfate reducing bacteria

The effect of sulfate reducing bacteria (SRB) upon the cathodic protection of XL 52 steel was determined, in order to identify if the potential value of ?0.950 V versus copper/copper sulfate electrode is good enough to protect the metal surface. During the experiments, different operational parameters were monitored: hydrogen sulfide production, iron concentration, electrolyte alkalinity, microorganisms' population, as well as the metal surface damage. At the same time, the corrosion rate was determined using two electrochemical techniques: polarization resistance (PR) and electrochemical impedance spectroscopy (EIS). According to the results, it was observed that the protection potential of ?0.950 V versus copper/copper sulfate electrode is not enough to control the microbiologically induced corrosion. This situation is reinforced by the fact that significant iron concentration was found in the electrolyte. The microbiological activity is not affected by the protection potential. On the contrary, the population growth is slightly strengthened. The alkalinity generated by the applied potential did not stop the SRB growth. A type of localized corrosion was developed during the experiments with microorganisms, even when the protection potential was applied to the system.     

锡电极嵌锂过程的交流阻抗谱

采用交流阻抗谱研究锡电极的首次嵌锂和第二次嵌锂过程,对比锡纳米阵列电极、锡薄膜电极和锡箔3种不同材料微观结构对电极交流阻抗谱特征的影响。用等效电路模型分析交流阻抗谱,得到嵌锂过程电化学特征参数与电位关系。结果表明:锡纳米阵列电极与锡薄膜、锡箔电极具有不同交流阻抗谱特征,锡纳米阵列电极在中频区出现双电层阻抗;首次嵌锂时在1.6~0.8 V之间形成固体电解质膜(SEI);电极材料微观结构显著影响锡电极的SEI膜电阻、Warburg阻抗和锂离子扩散速率;锡纳米阵列电极上的SEI膜电阻和Warburg阻抗最小,锂离子扩散能力最强;锡纳米阵列电极上锂的扩散系数为4.4×10-15~1.4×10-11 cm2/s;锂扩散系数随电位变化显著。     

Effect of 6-thioguanine,as an electrolyte additive,on the electrochemical behavior of an Al–air battery

In this study, the electrochemical behavior of an Al–air battery is improved by mixing 6-thioguanine into 4.0 M NaOH electrolyte. The electrochemical performance of the Al electrodes is analyzed using potentiodynamic polarization, potentiostatic oxidation, and electrochemical impedance spectroscopy. The surface morphology of the Al electrodes after discharging for 1,000 s is characterized using scanning electron microscopy coupled with X-ray elemental mapping for Al, O, C, N, and S. Furthermore, the utilization efficiencies of these samples are also determined. The results show that the corrosion resistance of the Al electrodes initially increases and then decreases with an increase in 6-thioguanine concentration. The presence of 6-thioguanine enhances the corrosion resistance to the maximum, with a corrosion current density (I_corr) of 6.170 mA/cm², and corrosion inhibition efficiency (η) of 36.56%, at 0.5 mM of 6-thioguanine.     

Improvement in corrosion resistance of commercial pure titanium for the enhancement of its biocompatibility

A new surface modification protocol encompassing an anodization treatment has been developed to improve the surface properties of biomedical titanium. Anodization in presence of nickel sulfate is one of a good way to improve the resistance of commercial pure titanium (cp‐Ti) in phosphate saline buffer solution (PSB). The potentiostatic behavior of anodized titanium in sulfuric acid with nickel sulfate differed markedly from that of titanium anodized in sulfuric acid free from nickel sulfate. Polarization and electrochemical impedance spectroscopy (EIS) recorded an increase in the corrosion resistance of the passive film. Scanning electron microscopy (SEM) and energy diffraction X‐ray (EDX) analysis were used to investigate the morphology and structure of the anodized film in absence and in presence of nickel sulfate. On the other hand, sealed anodized titanium samples exposed to PSB for up to 3 days have been studied by EIS to obtain detailed information concerning the electrochemical properties of sealed anodized titanium. An equivalent circuit that reproduces the impedance results of porous cp‐Ti oxide (TiO₂) films is proposed. These observations indicate that anodization of cp‐Ti in presence of nickel sulfate and sealing the anodized film can serve as a simple low‐temperature method to enhance the corrosion resistance of cp‐Ti when used as an implant material.     

Susceptibility of chloride ion concentration,temperature, and surface roughness on pitting corrosion of CoCrFeNi medium-entropy alloy

The influence and susceptibility of chloride ion concentration, temperature, and surface roughness on corrosion behavior of single-phase CoCrFeNi medium-entropy alloy (MEA) was examined in NaCl solution. Potentiodynamic polarization results revealed that the corrosion performance of the sample deteriorated with an increase of the chloride ion concentration, temperature, and surface roughness. The pitting potential decreased drastically for samples with higher surface roughness. According to electrochemical impedance spectroscopy, the charge transfer resistance decreased when chloride ion concentration, temperature, and surface roughness increased. Scanning electron micrographs also indicated an increased extent of corrosion damage, especially for the sample with higher surface roughness. It is found that the corrosion resistance is closely related to the wettability of samples, and the surface with the highest roughness shows higher hydrophilicity. The combined results suggested that the pitting damage is more sensitive to surface roughness. Our findings provide a further understanding of the corrosion mechanism of MEAs and guide their applications as structural materials.     

Electrochemical behavior of copper-nickel alloys in acidic chloride solutions

The electrochemical behavior of Cu-Ni alloys in acidic chloride medium was investigated. Commercial Cu-Ni alloys were investigated using potentiodynamic techniques, complemented by electrochemical impedance spectroscopy. The influence of alloy composition, chloride ion concentration and immersion time on the electrochemical response of the alloys was analyzed. Results of present investigations with pure metals (Cu and Ni) are also considered in this paper for the sake of comparison. Potentiodynamic measurements reveal that the increase in nickel content decreases the corrosion rate of the alloy and when the nickel content exceeds 30%, an increase in the corrosion rate was recorded. Also, the corrosion current density increases with increasing the concentration of chloride ions up to 0.6 M.The experimental impedance data were fitted to an equivalent circuit model representing the electrode/electrolyte interface. The relevance of the proposed model to the corrosion/passivation phenomena occurring at the electrode/solution interface was discussed.     

金属在流动氯化物体系中流动腐蚀的EIS研究

流动氯化物体系中碳钢、双相钢电极的电化学阻抗谱（EIS）明显不同,随着流速增大,电极表面受到的切应力增大,反应阻抗减小,电化学腐蚀加速,协同效应增强,结果使电极流动腐蚀速度增加,与碳钢相比,双相钢电极在较高流速下其电化学阻抗谱才在低频区发生特征变化,证明了曹楚南提出的不可逆电极阻抗谱理论同样适用于流动腐蚀过程中电极过程的研究,揭示了在流动体系中,当电极表面受到足够大的切应力作用时,在低频区电极电化学阻抗谱会发生特征改变,其中,电化学阻抗谱的低频感抗弧特征预示着在流动腐蚀过程中,受到强力流体力学作用的电极表面会改变其常规的溶解速度和溶解机制,同时表面伴随有坑、点局部腐蚀的发生,在此情况下,钝态金属电极的电化学阻抗谱进一步反映了电极表面受到固体颗粒摩擦或撞击的阻抗谱特征。