铁在含有SCN^—的高氯酸钠及硫酸钠溶液中的腐蚀电化学行为

利用稳态恒电流极化曲线测量研究了纯铁在除氧的SCN~- NaClO_4及SCN~- Na_2SO_4体系中(总离子强度1N)的腐蚀电化学行为。结果表明,铁在这两种体系中的腐蚀电化学行为相同。SCN~-在低浓度的情况下(C_(SCN)-≤0.05N),同时阻滞铁的阳极溶解及阴极析氢过程;SCN~-在较高的浓度下(C_(SCN)->0.1N)作为促进剂参与铁的阳极溶解过程,而阻滞阴极析氢过程。OH~-对铁的阳极溶解起促进作用。得到了铁在不同浓度的SCN~-范围内的阳极溶解及阴极析氢过程的动力学经验方程,提出了相应的反应机理。     

冷轧带钢电解清洗极板腐蚀机理和原因

采用线性电位扫描法研究了碳钢在不同脱脂剂浓度下的阳极极化过程,进一步研究了碳钢在不同不同脱脂剂浓度条件下、不同电位下的恒电位、恒电流电解行为,在此基础上对生产现场进行了考察。电化学实验表明：碳钢阳极极化过程依次经历活化区、钝化区、过钝化区及极限区;活化区基体活化溶解电流小,不影响电极寿命;过钝化区电极表面开始发生析氧反应;极限区析氧反应达到极限,使基体腐蚀反应大量发生,电极寿命降低;脱脂剂浓度越低、阳极电位越高,电极表面基体溶解反应速率越大,相应电极使用寿命越短。实际生产中,极板表面由于电流分布不均使其局部电流超过极限电流导致局部腐蚀发生,而电解槽内极板安装精度、电极表面气泡无法逸出、极板表面污泥淤积等都均会影响电流分布。     

有,无磁场下缓蚀剂对Fe／0.05mol.L^—1HCl极化行为的影响

研究指出，Ｆｅ／０．０５ｍｏｌ．Ｌ＾－１ＨＣｌ体系中引入不同的缓蚀剂有可能产生不同的阴极过程和阳极过程。磁场一般不影响Ｆｅ的阳极溶解过程。但在成膜过程中会增大阳极电流密度。磁场也不影响阴极过程中Ｏ２扩散，Ｓｎ＾２＋还原，Ｓｎ＾２＋扩散，镀Ｓｎ层上氢还原等反应，但会影响Ｆｅ上氢还原反应。动态分析了缓蚀剂和磁场同时存在下，阴极析氢过程中磁场效应与缓蚀剂的交互作用，给出此时覆盖度与磁场作用系数的关系式。     

氢对304不锈钢阳极行为的影响

虽然奥氏体不锈钢在42％MgCl_2沸腾溶液中的应力腐蚀并不是由氢致开裂引起的,但在应力腐蚀过程中生成的氢可以进入试样并可在裂纹前沿富集。为澄清进入试样的氢是否对阳极溶解过程产生促进作用,曾有人用失重法、晶间腐蚀和极化曲线变化等研究氢对阳极行为的影响,并得出氢促进阳极溶解的结论。应当指出,充氢试样的阳极电流包括了氢的氧化电流,因此充氢后阳极电流的增大并不证明氢促进了阳极溶解过程。虽然失重法能反映氢的促进作用,但只适用于腐蚀较为严重的情况。     

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.     

电解剥离过程中热镀锌合金化镀层的阳极溶解机制

分析了电解剥离过程中热镀锌合金化镀层的阳极溶解机制。结果表明,在GA镀层电解剥离的初始阶段,主要发生Zn的氧化,电解剥离过程中存在Zn和Fe之间的电耦合反应。由于镀层中微裂纹的存在,阴极反应区和镀层裂纹缝隙中会同时发生析氢反应,从而导致电偶腐蚀发生并形成诱导电流。当电解质溶液中存在氯离子时,Zn和Fe之间也会发生电耦合反应,该反应可以在一个非常小的局部区域内进行,反应过程中,氢的形核析出既可以是氢离子的重组,也可以是少量Zn和Fe的溶解反应。GA镀层中Fe-Zn金属间化合物同时发生电化学反应而溶解的现象只能在缝隙中发生,由于细小缝隙表面形成的活化区非常小,因此,GA镀层中的Fe-Zn相将分别发生溶解,从而保证了GA镀层中不同相之间的电压跃迁。     

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。     

外加电位对X70管线钢在库尔勒土壤模拟溶液中应力腐蚀开裂敏感性的影响

采用慢应变速率拉仲试验(SSRT)研究了不同外加电位下X70管线钢在库尔勒土壤模拟溶液中的应力腐蚀开裂(SCC)行为,并用扫描电镜分析了不同电位下的断面形貌.结果表明,X70管线钢在库尔勒土壤模拟溶液中具有SCC敏感性;在Ecorr附近施加弱极化时,应力腐蚀开裂敏感性增加;施加强阳极电位时,发生强烈阳极溶解,导致阳极溶解断裂;施加强阴极电位时,析氢过程加强,导致氢致应力腐蚀断裂.     

预变形对Q235钢在硫酸溶液中腐蚀行为的影响及硫脲的缓蚀作用

采用腐蚀失重、极化曲线和电化学阻抗谱(EIS)等方法研究了预变形对Q235钢在50℃硫酸溶液中腐蚀行为的影响及硫脲的缓蚀作用。结果表明:预变形Q235钢在有、无添加硫脲的硫酸溶液中的腐蚀速率均高于未变形Q235钢的腐蚀速率,硫脲对有、无预变形Q235钢的缓蚀作用均存在浓度极值效应;预变形加速了Q235钢在硫酸溶液中的阳极溶解和阴极的析氢反应,使电化学阻抗变小;硫脲对阳极反应的影响与电位区间有关,硫脲显著抑制阴极反应并表现出抑制作用的浓度极值效应。     

X70钢在乳酸溶液中的阴阳极反应机理研究

通过动电位扫描法和红外反射光谱法,研究了乳酸浓度对X70钢阴阳极反应速率的影响及其腐蚀机理.结果表明:乳酸浓度增大时,电离出更多的氢离子,促进阴极析氢反应,当浓度大到一定程度继续增大时,由于乳酸附着在X70钢的表面,阻碍氢离子得电子进程,所以阴极反应速度先增大后降低;乳酸阴离子附着在X70钢的表面对X70钢的溶解反应有一定的阻碍作用,使阳极反应速度随浓度的增大逐渐降低. 页     

Anodic dissolution of nickel in acidic chloride solutions

The anodic dissolution of nickel was studied galvanostatically in hydrochloric acid solutions of various concentrations. The reaction orders of chloride ion and hydrogen ion concentrations were found to be 0.5 and 1.0, respectively. An anodic Tafel slope equal to 120 ± 10 mV · decade⁻¹ was obtained. The dissolution rate of nickel at constant acid concentration was increased with stirring of the solution and increasing temperature. The activation energy, ΔH, for the anodic dissolution process was found to be 12 kcal · mol⁻¹. The presence of oxygen in solutions assisted the passivation process. The effect of addition of aniline and some of its derivatives (o-, m-, and p-anisidine) as inhibitors on the dissolution kinetics of Ni in 1 M HCl was also investigated. These compounds inhibited the anodic dissolution of nickel without affecting the Tafel slope, indicating that the adsorption of such inhibitors could not interfere with the mechanism of metal dissolution.     

On the electrochemical behaviour of tungsten: the formation and dissolution of tungsten oxide in sulphuric acid solutions

The formation and dissolution of the anodic oxide film of tungsten were investigated in sulphuric acid solution of different concentrations. The dissolution process was found to follow a first order mechanism under different conditions. It seemed that, in highly diluted solutions, the hydrate formation is favoured, whereas in concentrated solutions, the process takes place via the formation of WO₂²⁺. The rate of dissolution was found to increase by increasing the initial current density of formation.     

含H2S的硫酸溶液中Cl^—对铁阳极溶解的影响

应用电化学动电位扫描方法研究了在含低浓度Ｈ２Ｓ的硫酸溶液中Ｃｌ＾－对铁阳极溶解的影响。采用量子化学计算方法,得到了Ｃｌ＾－与ＨＳ＾－在电极表面吸附的稳定形态,优化计算了阳极电位下Ｃｌ＾－与ＨＳ＾－竞争吸附的总能量,结合能和Ｆｅ原子净电荷分布。     

Chemische und elektrochemische Reaktionen von Eisensulfid und Mangansulfid in sauren und neutralen Lösungen

Chemical and electrochemical reactions of iron sulfide and manganese sulfide in acid and neutral solutions The reactions which occur upon corrosion of massive iron sulfide and manganese specimens in perchloric acid and in neutral sodium chloride solution were elucidated by measurements of current-potential curves and by coulometric and analytical investigations on the processes. In acids the sulfides are dissolved by prevailing chemical reaction under evolution of H₂S. Upon applying anodic overpotentials electrochemical reactions occur simultaneously, however, with such low velocity that the contribution to corrosion of the sulfides is insignificant. Upon applying cathodic overpotentials some hydrogen discharge is observed on iron sulfide but not on manganese sulfide. In 3% sodium chloride solution both sulfides corrode very slowly upon anodic polarization, forming elementary sulfur according to MeS = Me²⁺ + S + 2e^? (Me = Fe or Mn). At high anodic potentials additional oxidation reactions occur in which three-valent iron and tetravalent manganese ions as well as sulfite and sulfate ions are formed. Iron sulfide and manganese sulfide inclusions can he isolated from steels only by electrochemical dissolution in neutral or weakly basic electrolytes, the potential during electrolysis must not be more positive than the corrosion potential of the sulfides.     

Effects of a magnetic field on the anodic dissolution, passivation and transpassivation behaviour of iron in weakly alkaline solutions with or without halides

The effects of a 0.4 T horizontal magnetic field on the anodic dissolution, passivation and transpassivation behaviour of iron in bicarbonate solutions of various concentrations and in dilute bicarbonate solutions with or without halides are investigated by electrochemical polarisation measurements. The applied magnetic field does not affect the activation-controlled anodic current, the steady passive current and the transpassive current, but significantly affects the activation-passivation transition processes for iron in bicarbonate solutions without halides. The effects of magnetic field are strongly dependent on passivation mechanisms that result in different types of surface films and corresponding rate determining steps of film dissolution. There is a synergistic effect between the applied magnetic field and halides, chlorides or bromides, on attacking the passivation of iron in dilute bicarbonate solutions. The effects of the magnetic field are analysed based on the previously proposed electrochemical kinetics equations. The magnetic field affects the anodic polarisation behaviour through its enhancing effects on mass transport processes at the precipitation-dissolution type surface film/solution interfaces. The magnetic field shows little or no effects on continuous and steady passivation films where the oxidation rate is controlled by mass transport processes within surface films. Magnetoelectrochemistry measurements are suggested as a prospective method for researches on corrosion or passivation mechanisms.     

硫酸溶液中硫脲对铁缓蚀作用的电化学和SERS研究

用表面增强拉曼散射（ＳＥＲＳ）光谱技术和电化学手段研究硫脲在硫酸体系中对铁的缓蚀作用，结果表明，硫脲对铁的缓蚀作用具有浓度极值现象。低２的硫脲通过活性点吸 抑制铁的阳极溶解，高２的硫脲参与铁伯最极溶解反应，奠定Ｌａｎｇｍｕｉｒ吸附等温式，动力学参数为ＶＴＵ＝１，ｂａ＝１１８ｍＶ，低浓度硫脲主要以平行吸附为主，高２硫脲则倾向于垂直吸附。     

Probing into the effects of a magnetic field on the electrode processes of iron in sulphuric acid solutions with dichromate based on the fundamental electrochemistry kinetics

The effects of an applied magnetic field on the electrode processes of iron in sulphuric acid solutions with dichromate have been investigated by electrochemical measurements. Open circuit potentials, cathodic and anodic polarisation curves, values of polarisation resistance were measured in the presence or absence of a 0.4 T horizontal magnetic field (HMF). A potentiostatic polarisation plus magnetic field perturbation technique was used to study the effect of the magnetic field on open circuit corrosion. Cathodic reaction rates at open circuit potentials for iron in sulphuric acid solutions containing dichromate ions are controlled by both the electron-transfer process and the diffusion process. A magnetic field made the open circuit potential move in the positive direction, and changes of the open circuit potentials due to the magnetic field increase with increasing dichromate concentration. When iron was potentiostatically polarised at open circuit potentials in the absence of a magnetic field, a cathodic current was observed after a magnetic field was imposed. Such cathodic currents induced by the magnetic field increases with increasing dichromate concentration. The positive shifts of open circuit potential, the decrease of polarisation resistance, and the occurrence of cathodic currents induced by the magnetic field are caused by the accelerating effect of magnetic field on the cathodic diffusion process. Measured current densities showed lower, equal, or higher values in the presence of the magnetic field than those in the absence of a magnetic field at certain anodic potentials. This effect of the magnetic field is related to the contribution of the cathodic and anodic reactions to the measured current and the types of rate-determining steps for each reaction at certain potentials. The applied magnetic field significantly decreased the polarisation resistance. The experimental results in this paper are formulated based on the fundamental electrochemistry kinetics after introducing a coefficient term of the magnetic field effect on the mass transfer process of reactive ions.     

不同电解温度下阳极氧化铝薄膜纳米孔的自组织过程

研究温度对阳极氧化铝薄膜纳米孔自组织过程的影响.使用环境扫描电镜(ESEM)研究了铝试样在硫酸、草酸、磷酸溶液中,于不同电解温度下阳极氧化形成的氧化铝薄膜形貌.通过分析阳极氧化时电流密度与时间关系曲线,研究了温度对阳极氧化铝薄膜纳米孔自组织过程的影响.提出降低电解温度能够缩短纳米孔自组织过程的时间,是由于降低电解温度增大了纳米孔内表面的表面张力.并且提出在不同的电解质溶液中,电解温度对纳米孔自组织过程的影响程度不同,电解温度对纳米孔自组织过程的影响以在硫酸溶液中最敏感,草酸次之,在磷酸溶液中的影响最小.     

含H2S的强酸性溶液中Cl^—对铁腐蚀的影响

应用化学动电位扫描和交流阻抗法研究了Ｈ２Ｓ的Ｈ２ＳＯ４溶液中Ｃｌ＾－对腐蚀的影响。结果表明，在含Ｈ２Ｓ的０．５ｍｏｌ／ＬＨ２ＳＯ４溶液中，Ｃｌ＾－１能同时抑制铁腐蚀的阴，阳极反应，且Ｃｌ＾－的抑制作用存在浓度极值现象，极值点为１ｍｏｏ／Ｌ；     

Effects of phenol, dioxane, and oxyethylidene diphosphonic acid on the oxide and nonoxide passivation of iron in acetate solution

Effects of phenol, dioxane, and OEDPh complexone, which form soluble complexes with Fe³⁺ cations, on the anodic passivation of iron in acetate solution and its nonoxide passivation, which is caused by lithium oleate, are studied by the methods of voltammetry and impedance measurements. Phenol, dioxane, and OEDPh promote the anodic dissolution of iron both in the aerated and deaerated solutions. Phenol and dioxane have no effect on the nonoxide passivation of iron. Oxygen and OEDPh disturb the nonoxide passivation, which is caused by lithium oleate.