磁场对铁在磷酸溶液中不同电位下阳极电流的影响

采用极化曲线和恒电位极化方法,研究了磁场对铁在0.5 mol/L H_3PO_4溶液中不同电位下阳极电流的影响。结果表明:0 T磁场下阳极极化曲线表现为典型的阳极溶解、溶解-钝化转变、稳态钝化和过钝化特征,0.4 T磁场下阳极极化曲线的活性溶解区范围扩大以至于没有出现钝化区;0 T磁场下极化后的铁电极表面相对均匀,而0.4 T磁场下极化后铁电极发生加速溶解,在其水平方向的两侧出现局部凹陷;在1.2～1.5 V高电位区间内铁电极表面产物膜向溶液的传质过程为阳极反应速率控制步骤时,施加磁场使得阳极电流密度显著增加,也加速了铁电极的局部溶解,施加或撤去磁场对析氧反应的影响不明显。     

金在硫酸介质中的钝化行为（英文）

采用不同电化学测试技术研究纯金和铂电极在硫酸溶液中的阳极行为。循环动电位法研究表明,金电极极化时会出现2个氧化峰和1个还原峰,而铂电极只有1个析氧反应峰出现。将硫酸浓度从0.5 mol/L增加到1mol/L时,金电极的峰电流密度增加2倍。动电位法研究表明,增加搅拌速度会提高金的钝化区域,而对铂电极无影响。2 h的恒电位法研究表明,在1mol/L硫酸溶液中,在3个不同的阳极电位极化下,1.4 V时金电极的腐蚀速率最低。电化学噪音技术测试研究表明,在16 h的电位衰退中,在恒电位极化时所形成的钝化膜已经溶解。     

Pb-Ag-Nd合金在H_2SO_4溶液脉冲电流极化过程中的电化学行为（英文）

采用计时电位、SEM、XRD、EIS和Tafel等方法对比研究Pb-Ag-Nd合金在160 g/L H2SO4溶液中的脉冲电流极化和恒电流极化过程中的氧化膜和析氧行为。研究结果表明:脉冲电流极化的Pb-Ag-Nd合金表面的氧化膜孔洞更少,膜层更致密。这是由于在脉冲电流极化过程中的低电流阶段析氧反应更缓和,有利于多孔氧化膜的修复,因此低电流阶段可作为氧化膜的"修复期"。Pb-Ag-Nd阳极在脉冲电流极化过程中表现出更低的阳极电位,这与脉冲电流极化过程中阳极更小的传荷阻抗和高过电位区间更小的Tafel斜率相对应。更低的阳极电位可能与其氧化膜中更高的PbO2含量有关,因为PbO2可以促进析氧反应活性位点的生成。     

铜锡合金阳极在熔融碳酸盐中氧化膜的形成及其防护性能

通过动电位扫描阳极氧化成膜、恒电位预氧化成膜以及开路电位浸泡预氧化成膜3种途径分别得到了3种氧化膜各有差异的QSn7-0.2铜锡合金电极。采用光学显微分析与XRD测试,表征了各氧化膜的形貌和成分,并且利用阳极极化曲线研究了3种成膜电极在450℃Li-Na-K三元共晶熔融碳酸盐中作为惰性析氧阳极的可行性。结果表明,恒电位预氧化成膜以及开路电位浸泡预氧化成膜两种成膜方法均能够在QSn7-0.2铜锡合金阳极表面形成含SnO_2的氧化膜,该膜能够显著阻碍基体合金中Cu的阳极溶解腐蚀,并且对析氧反应具有确定的电催化性能。     

N80碳钢CO2／HAc腐蚀电化学过程

采用动电位扫描、恒电位极化和电化学交流阻抗测试技术,研究了乙酸(HAc)对N80碳钢在50℃、饱和CO2的1%NaCl溶液中的电化学腐蚀行为的影响,并讨论了阴极、阳极的反应机理.研究表明:HAc能够直接在电极表面还原,使阴极极限电流增加.HAc未改变阳极反应机理,但能够加速中间产物的形成/溶解过程,从而加速阳极溶解过程.在饱和CO2溶液体系,乙酸盐易与碳酸生成HAc,而参与电化学反应.因此,无论是HAc还是乙酸盐均能够加速N80碳钢电极的CO2腐蚀.     

93%硫酸内碳钢在恒电流条件下的电位振荡

93％硫酸中处于阳极钝化状态下的碳钢电极,在转入较小极化电流的恒电流状态后,会发生很有规律的正弦波形的电位振荡现象。发生电位振荡的条件是:起初的恒电位极化电位等于或正于+300毫伏(相对于同一介质中的铂参比电极);接着的恒电流极化在电流密度的一定范围内电位振荡的幅度和周期都变化不大,但如低于临界值则不发生振荡。温度升高,振幅减小,周期变短。搅拌某一时间后使振荡消失。电位振荡是由于极化电流不足以维持稳定的钝态,局部表面膜反复地溶解和形成.从而导致活化-钝化交替变换。     

Ni合金化对Zn在3.5% NaCl溶液中阳极溶解行为的影响(Ⅱ):动电位、恒电位和恒电流研究（英文）

Zn是钢防腐常用的金属。进一步添加其他元素,如Ni,可以降低其腐蚀速率,保持其牺牲性保护作用。采用动电位、恒电位和恒电流技术研究Zn、Ni和不同Ni含量(0.5%~10%)的Zn-Ni合金在3.5%Na Cl溶液中的阳极溶解行为。利用EDX和SEM对Zn,Ni和Zn-Ni合金腐蚀层的成分和显微组织进行表征。恒电位曲线表明,所有研究电极的阳极行为都呈现活化/钝化转变,而且除99.5Zn-0.5Ni合金外,随着Ni含量的增加,合金的钝化趋势减弱。而动电位曲线表明,只有Zn表现出活化/钝化转变。表面分析表明,腐蚀产物主要为氧化物、氯化物和氢氧氯化物。与Zn相比,90Zn-10Ni合金中可观察到细微的裂纹。     

化学镀铟对锌在碱性溶液中电化学行为的影响

采用等离子体原子发射光谱(ICP)、扫描电镜(SEM)、线性电位扫描(LSV)、循环伏安(CV)和交流阻抗(EIS)等方法研究了化学镀铟对锌在碱性溶液中析氢和阳极溶解行为的影响.结果表明:化学镀铟能有效抑制锌自腐蚀共轭反应,即阴极析氢反应和锌的阳极溶解反应,并拓宽锌的活化电位区,延缓锌的钝化;厚度适宜的镀铟层能显著提高锌电极的可充性.     

镁海水电池阳极活化机理研究

研制了新型Mg-Hg-X合金阳极材料,用扫描电镜(SEM)、能谱、X-射线衍射(XRD)和电化学测试等方法分析了镁合金阳极材料在海水介质中腐蚀前后的微观结构、表面形貌及表面元素的组成,研究了Mg-Hg-X合金阳极的溶解过程及活化机理.结果表明:在放电初期,Mg-Hg-X合金阳极材料中的第2相粒子随点腐蚀的发生直接脱落,形成腐蚀坑,随后Mg-Hg-X合金阳极溶解在介质中的合金元素离子与基体镁发生反应,再沉积于镁阳极材料表面的点蚀孔中,形成Hg、X的沉积层,破坏钝化膜的结构,降低了Mg-Hg-X合金阳极极化.使电极电位负移,同时沉积的具有高析氢过电位的Hg、X抑制了析氢腐蚀.     

低驱动电位Al-Ga合金牺牲阳极及其活化机制

采用恒电流试验评价了不同Ga含量的Al-Ga二元合金牺牲阳极的电化学性能,并通过X射线衍射、扫描电镜及能谱分析、回沉积等实验探讨了阳极的活化溶解机制。结果表明,采用高纯铝锭炼制的Al-0.07%Ga 二元合金工作电位在-0.820 V~-0.876 V（vs.Ag/AgCl海水）之间,而用工业铝锭Al99.85炼制的Al-0.1%Ga二元合金阳极工作电位在 -0.802 V~-0.818 V之间,基本满足低驱动电位牺牲阳极的要求,但局部腐蚀溶解均较严重,溶解性能有待改善;Al-Ga合金腐蚀产物中的 Ga含量随基体中Ga含量的增加而增加,但远小于基体中的Ga含量;溶解后阳极表面的Ga含量大于基体中Ga含量,原因是溶解在溶液中的 Ga³⁺回沉积到阳极表面,使得阳极表面Ga含量增加;Al-Ga阳极的活化符合溶解-再沉积机理。     

Prevention of transpassive dissolution of austenitic stainless steel counter electrodes in nickel based electrolytic coloring solutions for anodized aluminum

In low nickel ion containing, weak acidic, electrolytic coloring solutions for anodized aluminium, austenitic stainless steel counter electrodes dissolve transpassively. The role of nickel and cobalt ions in preventing the transpassive dissolution of AISI Type 304 and 316 austenitic stainless steel counter electrodes was investigated. Potantiodynamic polarization method was used. The test solutions were a buffer (29.66 g/lt boric acid), a buffered supporting electrolyte (32.6 g/lt boric acid + 26.18 g/lt magnesium sulphate heptahydrate + 14,95 g/lt ammonium sulfate) and the coloring solutions (supporting electrolyte with different nickel (27.6–101 g/lt as heptahydrated sulfate) and cobalt (33–166 ppm) content). The oxidation of bivalent nickel ions starts 200 mV lower than the transpassive dissolution of stainless steel. However, even a small amount of cobaltous ions (165 ppm) in the solution produces a much steeper oxidation peak on the top of the nickel oxidation current. In order to transpassively dissolve a stainless steel electrode in cobalt containing nickel solutions, anodic current must be greater than the combined oxidation peak of nickel and cobalt ions, otherwise the working potential of the stainless steel electrode is always kept at the passive region hence the transpassive dissolution is prevented.     

An investigation on the effect of bleaching environment on pitting corrosion and transpassive dissolution of 316 stainless steel

Pitting corrosion and transpassive dissolution of 316 stainless steel in a solution containing five percent of commercial bleaching liquid was investigated by employing potentiodynamic polarization method and recording corrosion potential during immersion. Today commercial bleaching liquids are widely used as a cleaner additive. Therefore those house appliances made from stainless steels are in contact with aqueous solution containing bleaching liquid. This may cause severe localized corrosion and transpassive dissolution. In order to investigate the possibility of tranpassive dissolution of stainless steel by bleaching liquid, potentiodynamic polarization and recording the variation of corrosion potential of specimens were carried out in 0.2 M Na₂SO₄ solution containing 5%wt. commercial bleaching liquid. A 500 mV drop in transpassive potential and also instantaneously ennobled corrosion potential revealed the possibility of transpassive dissolution due to the oxidizing effect of the species such as free chlorine and its derivatives in bleaching liquid. Evaluation of the occurrence of localized corrosion at the presence of Cl^? and bleaching liquid was investigated by similar electrochemical experiments in 0.2 M Na₂SO₄ + 0.4 M NaCl containing 5%wt. bleaching solution. Initiation of stable pitting at potentials lower than the transpassive potential as well as a sharp increase of the corrosion potential in this environment demonstrates the possibility of pitting corrosion.     

Ni/LaNi5多孔复合电极的制备及其析氢电催化性能

先电沉积Ni-Zn合金镀层,然后用浓碱将镀层中的锌脱溶,得到多孔镍,最后采用复合电沉积将LaNi5镶嵌到多孔镍表面,制备成Ni/LaNi5多孔复合电极。采用稳态极化曲线和交流阻抗谱对电极的电催化析氢性能进行了评价,并运用恒电位间歇电解和长时间电解,开路电位等研究了电极的电析氢稳定性。结果表明:Ni/LaNi5多孔复合电极的析氢表观交换电流密度分别是镍和多孔镍的172倍和26倍;多孔复合电极中的LaNi5具有稳定电极的作用,该电极比多孔镍具有更优异的抗断电性能。     

The polarization behaviour of chromium in acidic sulphate solutions

The polarization behaviour of chromium was studied in solutions of various pH, with particular regard to the hydrogen evolution reaction and chromium dissolution. Hydrogen evolution occurred on active and passive chromium and the exchange current density was ca. 10^?6 A/cm² at pH 1.0 on both electrodes. The rate of active dissolution of chromium did not depend on pH, an observation that indicated the absence of a hydroxyl-containing intermediate in the rate determining step. The transpassive dissolution of chromium was strongly dependent on pH, and it was suggested that the rate was controlled by a base-accelerated anodic dissolution of an oxide film.     

High rate anodic dissolution in chloride solutions of steel after electrothermochemical treatment

High rate (up to 15 A/cm²) anodic dissolution of St3 steel in chloride solutions (1–6 M NaCl) was investigated after its electrothermochemical al treatment (nitriding and thermal treatment). Various potential ranges (or current density ranges) can be emphasized: the region of anodic anion activation (sublimiting currents), the diffusion limitation area (caused by salt passivation), and the transpassive dissolution region. It is shown that the heat treatment influence is the most substantial in the region of salt passivation (or the limiting current region). The double role of the hydrodynamics is revealed during dissolution under these conditions: the influence of the ionic mass transfer rate in the solution and of the removal of the hard carbonaceous products produced as a result of the selective dissolution of the components of the nitrided steel. It is shown that, in sublimiting currents and transpassive dissolution ranges, the specific dissolution rate depends on the nitrogen content of the studied steel.     

Corrosion Behaviour of Manganese-Containing Stainless Steels. II. Potentiodynamic measurements in H2SO4 solutions

The behaviour of steels with (%) 17.3 Cr, 5.3 Ni, 0.3–13.9 Mn during potentiodynamic polarization k tests is comparable to that of 18 8 CrNi steels. Sharp peaks are found in the polarization curves; they correspond to the dissolution of the iron base: This region is followed by a passive zone characterized by low and potential-independent current flow. At a certain potential, however, a steep current rise sets in. In diluted acid there is even a transpassivity zone corresponding to the dissolution of Cr and Mn. The beginning of this zone corresponds to the beginning of the steep current rise in more concentrated solution. Cyclic cathodic reduction and anodic oxidation results in a considerable reduction of the height of the peaks in the active region, while this treatment has no effect on the transpassive region. The optimum composition of a steel would be (%) 17.3 Cr, 5.3 Ni, 5.6 Mn; higher Mn contents deteriorate the corrosion behaviour.     

The transpassive dissolution mechanism of highly alloyed stainless steels: I. Experimental results and modelling procedure

The transpassive dissolution of austenitic stainless steels (AISI 316L, AISI 904L, 254SMO and 654SMO) in a 0.5 M sulphate solution with pH 2 was studied by conventional and rotating ring-disc voltammetry, as well as electrochemical impedance spectroscopy. The main process in the transpassive potential region was found to be the release of soluble Cr(VI), while small amounts of lower-valency Cr or Mo species are released as well. Secondary passivation readily occurs for AISI 316L, whereas the remaining highly alloyed steels dissolve at high current densities in the whole potential range studied. The dissolution rate was found to increase in the order AISI 904L<254SMO<654SMO. Thus it can be correlated to the increase in the Cr and especially Mo content of the steel substrate. The impedance spectra contain contributions from the transpassive dissolution of Cr and secondary passivation, probably due to enrichment of Fe in the outermost layer of the surface film. A kinetic model of the process is proposed, including a two-step transpassive dissolution of Cr via a Cr(VI) intermediate and the dissolution of Fe(III) through the anodic film. The model was found to be in quantitative agreement with steady state current vs. potential curves and electrochemical impedance spectra. The kinetic parameters of transpassive dissolution were determined and the relevance of their values is discussed.     

The transpassive dissolution mechanism of highly alloyed stainless steels: II. Effect of pH and solution anion on the kinetics

The transpassive dissolution of austenitic stainless steels (AISI 316L, AISI 904L, 254SMO and 654SMO) in a 0.5 M sulphate solution with pH 2 was studied by conventional and rotating ring–disc voltammetry, as well as electrochemical impedance spectroscopy. The main process in the transpassive potential region was found to be the release of soluble Cr(VI), while small amounts of lower-valency Cr or Mo species are released as well. Secondary passivation readily occurs for AISI 316L, whereas the remaining highly alloyed steels dissolve at high current densities in the whole potential range studied. The dissolution rate was found to increase in the order AISI 904L<254SMO<654SMO. Thus it can be correlated to the increase in the Cr and especially Mo content of the steel substrate. The impedance spectra contain contributions from the transpassive dissolution of Cr and secondary passivation, probably due to enrichment of Fe in the outermost layer of the surface film. A kinetic model of the process is proposed, including a two-step transpassive dissolution of Cr via a Cr(VI) intermediate and the dissolution of Fe(III) through the anodic film. The model was found to be in quantitative agreement with steady state current vs. potential curves and electrochemical impedance spectra. The kinetic parameters of transpassive dissolution were determined and the relevance of their values is discussed.     

Effects of alternating current on corrosion of a coated pipeline steel in a chloride-containing carbonate/bicarbonate solution

In this work, the alternating current (AC)-induced corrosion of a coated pipeline steel was studied in a chloride-containing, concentrated carbonate/bicarbonate solution, which simulated the trapped high pH electrolyte under coating, by potentiodynamic polarization measurements, immersion tests and surface characterization technique. It was found that an application of AC resulted in a negative shift of corrosion potential of the steel, caused an oscillation of anodic current density, and degraded the steel passivity developed in the solution. With the increase of AC current density, the corrosion rate of the steel increased. At a low AC current density, a uniform corrosion occurred, while at a high AC current density, pitting corrosion occurred extensively on the steel electrode surface. At individual applied AC, there was a higher electrochemical dissolution activity of the coated steel electrode containing a 1 mm defect than that of the electrode containing a 10 mm defect.     

Acoustic emission during the electrochemical corrosion of 304 stainless steel in H2SO4 solutions

Acoustic emission (AE) behaviour during the electrochemical corrosion of 304 stainless steel (304SS) in H₂SO₄ solutions was studied. AE signals which related to transpassive dissolution are detected in solutions with low pH, and are very slightly influenced by current density and pre-strain. During hydrogen bubble evolution, a weak correlation exists between the AE signal amplitude and the hydrogen bubble diameter. The concept of potential – pH – AE diagram is proposed and such a diagram is drawn based on AE activity and b-values. The main mechanisms of AE sources which are transpassive dissolution and hydrogen bubble evolution, are also discussed.