On the Reactivity of Silver Electrodes in a Chlorine Radiofrequency Plasma — Plasma Oxidation vs. Thermal Oxidation

The plasma‐electrochemical growth of an ion‐conducting film by the oxidation of a metal in an electronegative plasma is investigated and compared with results from thermal oxidation. As model system we studied the oxidation kinetics of silver electrodes in a Cl₂ rf plasma. The electrochemical control of the reaction by external currents through the product layer using the plasma as a fluid electrode was achieved. Both potentiostatic and galvanostatic control of the reaction was applied. The morphology of the product layer and its temporal evolution was investigated using SEM. A formation of silver chloride surface patterns in the oxidation process takes place if a simple stability criterion is not fulfilled. Specific surface morphologies were found under different experimental conditions. The morphology of the product layer is influenced by the external electric current and the substrate temperature. The influence of the plasma phase on the thermodynamics and kinetics of the oxidation process is discussed. The role of excited plasma species, the electrical charging of the surface and radiation from the plasma are taken into account.     

铂基Pb-Sb表面合金电催化剂的制备与结构表征

通过电化学方法,在玻碳载体表面制备以Pt、Pb、Sb为主要成分的铂基Pb Sb表面合金电催化剂.运用电化学循环伏安、石英晶体微天平（EQCM）和扫描隧道显微镜（STM）技术对催化剂电极进行表征.结果表明：酸性溶液中在所制备的表面合金电极上,析氢起始电位负移至－0.45 V,表面合金的起始氧化电位为0.15 V,其稳定性明显高于电催化还原中常用的铅、锑等金属电极.通过EQCM研究表面合金电极的形成过程,结合STM观察和XPS深度剖析,确定电催化剂表面是由粒度均匀的纳米颗粒构成的表面合金层.     

Physicochemical and electrochemical hydriding–dehydriding characteristics of amorphous MgNi x (x=1.0, 1.5, 2.0) alloys prepared by mechanical alloying

 Physicochemical and electrochemical hydriding-dehydriding characteristics of amorphous MgNi _x (x=1.0, 1.5, 2.0) alloys prepared by mechanical alloying have been investigated. It was found that the increase of Ni content in the alloys resulted in greatly enhanced kinetics for both absorption and desorption of hydrogen, while the saturation capacity showed the reverse tendency. Charge–discharge tests showed that the increase in Ni content lead to a significant enhancement in cycle performance of MgNi _x alloy electrodes. X-ray photoelectron spectroscopic and X-ray excited Auger electron spectroscopic investigations indicated the existence of a significantly thicker Ni-enriched layer for the MgNi_1.5 and MgNi_2.0 alloys than for the MgNi alloy. These results reveal that excess of Ni in MgNi _x alloys may improve the cycle performance of alloy electrodes by suppressing the segregation of Mg during electrochemical cycling, and the Ni in the topmost surface layer is mainly responsible for the improvement in the kinetics of hydrogen absorption. Received: 28 August 1999 / Accepted: 23 November 1999     

铁铬合金摩擦破损微电偶的形成及作用

本文分析，研究了１Ｃｒ１８合金材料在０．２ｍｏｌ．Ｌ＾１Ｈ２ＳＯ４溶液中的摩擦腐２蚀过程中产生微电偶腐蚀的可能性及原因，并研究了微电偶对摩擦电化学行为的影响，研究结果表明：由于摩擦过程造成材料表面的电化学不均一性是产生微电偶作用的真正原因。未摩擦表面与摩擦表面的面积比显著地影响了摩擦电偶电位和摩擦电偶电流的大小。     

Electrochemical control of adsorption dynamics of surface layer proteins on gold

The kinetics and mechanism of the adsorption of the surface layer proteins of Lysinibacillus sphaericus CCM2177 on gold depend on the charging conditions of the electrochemical double layer and the addition of Ca(2+) ions. The electrical and mass charging was monitored by an in situ electrochemical quartz microbalance. Adsorption and monolayer formation of the protein molecules occur in the positive potential region where solvated anions form the electrochemical double layer. The crystalline character of the surface layer was diagnosed by an atomic force microscope. Negative of the point of zero charge, multilayer island structures were found.     

非金属与金属的协同作用对镁基储氢合金电化学性能的影响

用机械球磨法分别以Ti、B、复合物TiB对非晶态Mg45Ti3V2Ni50储氢合金进行了表面修饰.实验结果表明,恰当比例的TiB球磨修饰对镁基储氢合金循环稳定性远好于Ti、B同比例单独修饰合金电极的效果.Mg45Ti3V2Ni50与TiB质量比为2∶1的Mg45Ti3V2Ni50-TiB(2∶1)复合合金电极的初始放电容量为529.4mAh·g-1,第50次循环放电容量仍为277.1mAh·g-1.复合物TiB中Ti、B元素之间和复合合金中合金元素与TiB之间产生了金属与非金属的协同作用,导致复合合金新的立体褶皱结构的生成,增强了修饰层与合金间的作用,Mg45Ti3V2Ni50-TiB(2∶1)合金电极表面活性增强,循环稳定性显著提高.     

Corrosion behaviour of mechanically polished AA7075‐T6 aluminium alloy

In the present study, the effects of mechanical polishing on the microstructure and corrosion behaviour of AA7075 aluminium alloy are investigated. It was found that a nano‐grained, near‐surface deformed layer, up to 400 nm thickness, is developed due to significant surface shear stress during mechanically polishing. Within the near‐surface deformed layer, the alloying elements have been redistributed and the microstructure of the alloy is modified; in particular, the normal MgZn₂ particles for T6 are absent. However, segregation bands, approximately 10‐nm thick, containing mainly zinc, are found at the grain boundaries within the near‐surface deformed layer. The presence of such segregation bands promoted localised corrosion along the grain boundaries within the near‐surface deformed layer due to microgalvanic action. During anodic polarisation of mechanically polished alloy in sodium chloride solution, two breakdown potentials were observed at ?750 mV and ?700 mV, respectively. The first breakdown potential is associated with an increased electrochemical activity of the near‐surface deformed layer, and the second breakdown potential is associated with typical pitting of the bulk alloy. Copyright © 2009 John Wiley & Sons, Ltd.     

电化学方法测定氢在TiNi貯氢合金中的扩散系数

在20±0.3 ℃时, 用电化学方法测得氢在TiNi贮氢合金中的扩散系数为(6.45±0.78)×10~(-7)cm~2sec~(-1), 氢在这种合金中扩散过程的活化能为16.59 kJ mol~(-1)。TiNi合金电极在NaOH溶液中, 经过多次电化学渗氢以后, 在合金表面覆盖着一层钛的氧化物, 在这氧化物层的下面为富镍层。     

镁合金表面微结构阵列的电化学微加工

研究了镁合金的约束刻蚀微加工方法. 通过对电解过程中电极表面氢离子浓度变化以及刻蚀体系对镁合金的腐蚀速率的测量与分析, 对一些可能有刻蚀作用的刻蚀体系进行了研究. 选用亚硝酸钠作为产生刻蚀剂(硝酸)的前驱体、氢氧化钠作为捕捉剂、少量硅酸钠作为缓蚀剂的约束刻蚀体系, 使用具有规整三维微立方体点阵结构的模板, 在金属镁表面加工出具有与模板互补特性的点阵微结构, 复制加工的分辨率为亚微米级. 并对刻蚀过程机理进行了探讨与分析.     

不同碱溶液表面处理对稀土镁镍基储氢合金的影响

采用相同浓度即6 mol·L^-1 LiOH、NaOH和KOH对稀土镁镍基储氢合金进行表面处理,研究了不同碱溶液和不同处理时间对合金表面形貌、组成和电极电化学性能的影响。研究表明,合金经6 mol·L^-1 NaOH溶液处理10 min后具有最好的综合电化学性能。但随着处理时间的延长,采用6 mol·L^-1 NaOH溶液处理的合金放电容量衰减明显,实验证明这是由合金表面稀土元素和Al元素的大量溶解进入碱溶液造成的。3种碱溶液比较,LiOH溶液能有效去除合金表面镁元素减少合金在碱溶液处理过程中的氧化,虽然形成的表面不利于H在合金表面的吸脱附,却能有效提高合金在碱溶液中的抗腐蚀能力,提高合金的循环稳定性。     

金属锌表面膜形成的椭圆偏振技术研究

介绍了近年作者课题组使用椭圆偏振技术研究金属锌表面氧化膜的形成,包括多晶锌表面自然氧化物薄膜的形成及其光学性能和电子结构、不同气氛自然氧化物膜的生长研究以及在碱性碳酸盐介质金属锌的电化学过程等方面的工作. 旨在通过原位和非原位椭圆偏振技术了解金属锌表面氧化物膜层的光、电性能以及膜层结构的改变和生长动力学,这对评估锌氧化层的总体性能有着重要意义.     

Catalytic reduction of TFSI-containing ionic liquid in the presence of lithium cations

The influence of the electrochemical double layer (EDL) structure on the electrochemical processes in ionic liquids is an intriguing subject. The complex layered structure of the EDL and its restructuring have been shown to strongly affect metal deposit morphology and electrochemical reaction kinetics. In this work, we demonstrate that the breakdown of an ionic liquid containing TFSI anions can be catalyzed through the addition of Li⁺ cations. We ascribe this catalytic effect to the change in the EDL structure: the Li⁺ cations preferentially adsorb on the electrode surface and drag the TFSI anions with them, facilitating their reduction. The decomposition of the ionic liquid leads to the formation of an SEI layer, which is studied using an electrochemical quartz crystal microbalance.     

高择优锌-镍合金电沉积的现场ECSTM研究

采用"二步包封"法制备了性能良好的电化学STM针尖.以此为基础采用ECSTM现场研究了工艺条件下HOPG上高择优锌-镍合金的电沉积过程.研究结果表明这种高择优沉积层以侧向生长方式生长,而表面上电化学活性差的晶面构成了晶体生长过程的保留面,从而进一步形成了与基底表面方向一致的高择优沉积层,X射线研究表明这一择优面为(100)晶面.     

The local electrochemical behavior of the AA2098-T351 and surface preparation effects investigated by scanning electrochemical microscopy

In this work, scanning electrochemical microscopy (SECM) measurements were employed to characterize the electrochemical activities on polished and as-received surfaces of the 2098-T351 aluminum alloy (AA2098-T351). The effects of the near surface deformed layer (NSDL) and its removal by polishing on the electrochemical activities of the alloy surface were evaluated and compared by the use of different modes of SECM. Confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM) were also employed to characterize the morphology of the surfaces. The surface chemistry was analyzed by X-ray photoelectron spectroscopy (XPS). The surface generation/tip collection (SG/TC) and competition modes of the SECM were used to study hydrogen gas (H₂) evolution and oxygen reduction reactions, respectively. H₂ evolution and oxygen reduction were more pronounced on the polished surfaces. The feedback mode of SECM was adopted to characterize the electrochemical activity of the polished surface that was previously corroded by immersion in a chloride-containing solution, in order to investigate the influence of the products formed on the active/passive domains. The precorroded surface and as-received surfaces revealed lower electrochemical activities compared with the polished surface showing that either the NSDL or corrosion products largely decreased the local electrochemical activities at the AA2098-T351 surfaces.     

Electrochemical characterization of solid materials in volume range II. Physical process parameters in phase isolation process

In this paper, the electrochemical phase isolation (EPI) is discussed as a process at higher current densities in which the desirable enrichment of precipitated phase particles leads to a blocking of the surface. This effect impedes the matrix dissolution rate. Under galvanostatic conditions, a higher current causes a heat build-up within the porous layer and accelerates the kinetics up to the moment when the saturation concentration is reached in the pores. Under this aspect, experiments for iron carbide isolation from a steel matrix are described.     

Kinetics of surface segregation of bismuth atoms at the interface of a mechanically renewable Ag-Bi alloy electrode with a surface-inactive electrolyte solution

The time effects observed on mechanically renewed electrodes of eutectic-type Ag-Bi alloys in NaF solutions in the potential range of ideal polarizability are studied by the impedance method and cyclic voltammetry. The changes in the electric double layer (EDL) capacitance observed with the increase in the time of the electrode-solution contact from the moment of electrode renewal indicate that the process of surface enrichment with Bi atoms occurs. The analysis of obtained data leads to a conclusion that the surface segregation of Bi proceeds by the mechanism of surface diffusion, which provides the anomalously high diffusion rates as compared with the processes of volume diffusion in the solid phase. The results of studies of the surface segregation of bismuth on the Ag-Bi alloy/electrolyte interface are compared with the Auger-spectroscopic data for the interface of the same alloy with vacuum. Assumptions are put forward and substantiated that allow the differences in the kinetics of surface segregation processes observed on different interfaces to be consistently interpreted.     

CR传输线解析EIS表征杯芳烃离子选择电极

电化学阻抗谱(EIS)是表征电化学体系特征及其过程机理的重要技术,但解谱模型不一致限制了其应用.为此,采用CR传输线模型中的8CRR等效电路拟合文献报道的杯[4,8,12]芳烃离子选择电极与Na+、Ca2+及Fe3+作用的EIS;并根据电荷转移电阻、表面吸附、扩散阻力和空间电荷层电容等不同特征,揭示了作用机理的共性与差异.结果表明,所采用的方法可操作性强,结果客观,具有一定的理论和应用价值.     

An in situ STM/AFM and impedance spectroscopy study of the extremely pure 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate/Au(111) interface: potential dependent solvation layers and the herringbone reconstruction

The structure and dynamics of the interfacial layers between the extremely pure air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate and Au(111) has been investigated using in situ scanning tunneling microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and atomic force microscopy measurements. The in situ scanning tunnelling microscopy measurements reveal that the Au(111) surface undergoes a reconstruction, and at -1.2 V versus Pt quasi-reference the famous (22 × √3) herringbone superstructure is probed. Atomic force microscopy measurements show that multiple ion pair layers are present at the ionic liquid/Au interface which are dependent on the electrode potential. Upon applying cathodic electrode potentials, stronger ionic liquid near surface structure is detected: both the number of near surface layers and the force required to rupture these layers increases. The electrochemical impedance spectroscopy results reveal that three distinct processes take place at the interface. The fastest process is capacitive in its low-frequency limit and is identified with electrochemical double layer formation. The differential electrochemical double layer capacitance exhibits a local maximum at -0.2 V versus Pt quasi-reference, which is most likely caused by changes in the orientation of cations in the innermost layer. In the potential range between -0.84 V and -1.04 V, a second capacitive process is observed which is slower than electrochemical double layer formation. This process seems to be related to the herringbone reconstruction. In the frequency range below 1 Hz, the onset of an ultraslow faradaic process is found. This process becomes faster when the electrode potential is shifted to more negative potentials.     

The interface electrochemical and chemical mechanism of a low alloy steel in a 3.5% NaCl solution containing Ce3+‐based inhibitor

The interface electrochemical and chemical mechanism of the low alloy steel in a 3.5% NaCl solution containing the Ce³⁺‐based inhibitor was investigated by the electrochemical techniques in conjunction with the surface analysis technologies. It was shown that the Ce^3+‐based inhibitor was an anodic inhibitor with more than 90.0% inhibitory efficiency. The net‐shaped inhibiting film with 200 to 500‐nm greyish balls was observed on the specimen surface. During the corrosion reaction occurred on the surface of the low alloy steel, the hydrolysis reaction of P₃O₁₀⁵⁻ and the disproportionation reaction of Ce³⁺ ions simultaneously occurred, too, resulting in the formation of the net‐shaped inhibiting film with nano‐scale greyish ball‐type products, which contained Ce element and had an obvious effect on the electrochemical process of the low alloy steel in a 3.5% NaCl solution containing the Ce³⁺‐based inhibitor. Therefore, the EIS spectra of the low alloy steel in a 3.5% NaCl solution containing the Ce³⁺‐based inhibitor were composed of a capacitive loop at a high‐frequency region and an inductive impedance loop at a low‐frequency region. The charge‐transfer resistance (R_t) increased with the immersion elapsed time, indicating that the inhibition efficiency of the Ce³⁺‐based inhibitor increased with immersion elapsed time. The calculated data based on the fitted electrochemical parameters showed the partial coverage of the inhibitor. This was further revealed by the analysis of electrochemical kinetics that the inductive impedance (L) loop at a low frequency region resulted from the localized absorption of the Ce³⁺‐based inhibitor on the surface of the low alloy steel in a 3.5% NaCl solution. It was also verified by micro‐morphologies.     

Influence of acidic ionic liquids as an electrolyte additive on the electrochemical and corrosion behaviors of lead-acid battery

The aim of this study is to introduce the application of some acidic ionic liquids (ILs) as an electrolyte additive in lead-acid batteries. A family of alkylammonium hydrogen sulfate ILs, which are different in the number of alkyl chain, is investigated with the aim to compare their effects on the electrochemical behavior of Pb–Sb–Sn alloy in sulfuric acid solution. The hydrogen and oxygen gas evolution potential and anodic layer characteristics were investigated employing cyclic and linear sweep voltammetric methods. The morphological changes of the PbSO₄ layer that formed on the electrode surface were confirmed using scanning electron microscopy. Also, potentiodynamic polarization curves, electrochemical impedance spectroscopy, and an equivalent circuit analysis were used to evaluate the corrosion behaviors of the Pb–Sb–Sn alloy in the presence of ILs. The obtained results indicate that hydrogen and oxygen evolution overpotential of lead–antimony–tin alloy increases in the solution containing IL and mainly depends on the number of alkyl chain in alkylammonium cation. It is clearly observed that the morphology of PbSO₄ layer changes under the influence of ILs. The corrosion studies show an increase in corrosion resistance of lead alloy in the presence of some ILs. Also, the electrochemical effects of ILs in conversion of PbSO₄ to PbO₂ and vice versa were investigated by carbon-PbO paste electrode. Cyclic voltammogram of carbon-PbO electrode shows that in the presence of ILs, oxidation and reduction peak currents increase, while reversibility decreases.