硼酸—硼砂缓冲液中铁的孔蚀及缓蚀剂PC—604作用的光电化…

采用光电化学方法对纯铁在ｐＨ＝８．４的硼酸－硼砂缓冲液中的孔蚀现象及缓蚀剂ＰＣ－６０４的作用进行了研究。结果表明，加入不同量的缓蚀剂后，铁表面钝化膜的禁带宽度没有发生变化，但是光电流信号却随缓蚀剂量的增加而增大了。从光电流暂态谱的研究中首次提出了钝化膜的膜参数的概念，并用以衡量钝化膜的抗孔蚀能力。     

光电化学方法研究不锈钢钝化膜的局部破坏

建立了评价钝化膜稳定性的光电化学方法——电位台阶光电流测量和恒电位光电流响应测量。研究了铁素体高铬不锈钢25Cr和奥氏体不锈钢AISl304,316L,321在0.1mol/LNaCI溶液中钝化膜的局部破坏及十二烷基苯磺酸钠和癸胺对AISI304不锈钢孔蚀的抑制作用。结果表明:钝化膜破坏后光电流增加;电位台阶光电流测量得出光电流开始突增的电位值与钝化膜的击穿电位对应,钝化膜破坏后光电流i_(ph)随电极电位增加值△E_b的变化规律可以反映钝化膜破坏的本质;缓蚀剂的加入改变了AISI304不锈钢i_(ph)     

复杂钝化体系P－G响应特征的研究

采用恒电位－恒电流（Ｐ—Ｇ）瞬志响应技术研究了多层结构钝化膜和存在吸附层钝化膜的复杂钝化体系提出了判断钝化膜多层结构的方法以及表征钝化膜不同层稳定性的特征参数，并建立了描述复杂钝化体系Ｐ—Ｇ响应特征的数学模型．研究了２２０５和３１６Ｌ不锈钢在２．５ｍｏｌ／ＬＨ２ＳＯ４中钝化膜的结构，以及吸附型缓蚀剂哌啶和癸胺对３０４不锈钢在０．５ｍｏｌ／ＬＮａＣｌ介质中孔蚀的抑制作用研究结果证实所建立的模型能很好地反映研究体系的Ｐ—Ｇ响应特征．利用提出的特征参数随极化电位和极化时间的变化关系，有效地分析了钝化膜的生长规律和稳定性，以及缓蚀剂对孔蚀发生与发展过程的抑制作用     

原子力显微镜对钢筋表面钝化膜的研究

利刚原子力显微镜(AFM)对钢筋在模拟混凝土孔溶液中形成的钝化膜开展研究。结果表明,AFM是研究钝化膜微观结构和表面形貌的有力工具;钢筋钝化胶是有缺陷的;复合缓蚀剂可以改善钢筋钝化膜的微观结构和表面形貌从而提高抗点蚀的能。     

用光电化学的方法研究模拟混凝土孔溶液中缓蚀剂对钢筋钝化膜的影响

采用光电化学的方法研究了复合缓蚀剂对钢筋钝化膜的影响.结果表明复合缓蚀剂的加入没有改变钢筋钝化膜的晶体结构和电子性质,它仍然是无定形n型的半导体成相膜,但对抑制点蚀核的形成有明显作用,且对钝化膜的生长速度有加快作用,从而有可能使钝化膜的组成发生改变.     

电化学阻抗谱法对304不锈钢孔蚀生长和再钝化阶段的原位研究

利用动电位电化学阻抗谱(DEIS)法研究了304不锈钢在0.1mol/L NaCl溶液中的孔蚀行为,比较了孔蚀前后钝化膜的电化学阻抗谱的变化。提出了一种改进的双层膜结构,用以评价不锈钢在孔蚀的初始阶段和再钝化阶段各个参数的不同,指出孔蚀对钝化膜外层破坏较内层严重。使用活化控制的膜破裂模式评价孔蚀的初始阶段和再钝化阶段各个参数变化。     

用光电化学的方法研究模拟混凝土孔溶液中缓蚀剂对钢筋钝化 …

采用光电化学的方法研究了复合缓蚀剂对钢筋钝化膜的影响。结果表明复合缓蚀剂的加入没有改变钢筋钝化膜的晶体结构和电子性质，它仍然是无定形ｎ型的半导体成相膜，但对抑制点蚀核的形成有明显作用，且对钝化膜的生长速度有加快作用，从而有可能使钝化膜的组成发生改变。     

敏化1Cr18Ni9Ti不锈钢钝化膜的光电流谱研究

采用评价钝化膜稳定性的光电化学方法－光电流谱技术，研究敏化不锈钢的钝化膜。光电流谱测试结果表明，对敏化的不锈钢电极，在不同的电位范围内，钝化膜显示出ｎ型或ｐ型半导体的特性。这可以用不同电位下不锈钢钝化膜组分中Ｃｒ水合程度的不同和表面态的存在来解释。本工作表明，光电流谱技术对于研究不锈钢敏化是很有用的工具。     

复杂钝化体系P-G响应特征的研究

采用恒电位-恒电流(P—G)瞬志响应技术研究了多层结构钝化膜和存在吸附层钝化膜的复杂钝化体系提出了判断钝化膜多层结构的方法以及表征钝化膜不同层稳定性的特征参数,并建立了描述复杂钝化体系P—G响应特征的数学模型.研究了2205和316L不锈钢在2.5mol/LH2SO4中钝化膜的结构,以及吸附型缓蚀剂哌啶和癸胺对304不锈钢在0.5mol/LNaCl介质中孔蚀的抑制作用研究结果证实所建立的模型能很好地反映研究体系的P—G响应特征.利用提出的特征参数随极化电位和极化时间的变化关系,有效地分析了钝化膜的生长规律     

氢对纯镍钝化膜的影响

研究了氢对纯镍阳极极化和钝化膜形成及耐蚀性能的影响。结果表明：预充氢会降低纯镍的自腐蚀电位,使其出现明显的活化区和临界钝化电流,缩短钝化区域;提高钝化电流密度和延长钝化膜的形成时间。固溶氢降低钝化膜的稳定性,增大膜的自活化能力;并导致钝化膜出现明显的孔蚀,膜的孔蚀电位随固溶氢含量的增加而降低。     

Dissolution, passivity and its breakdown on iron whisker crystals

The anodic polarization behaviour of iron whisker crystals was investigated in a neutral solution with or without the presence of chloride ion, with special attention to the role played by surface defects in the dissolution, the passivation and the pitting of iron. The grown whisker used was substantially dislocation-free and the defect density was varied by twisting of whisker. With increase in the angle of twisting, the anodic dissolution current increased in a chloride-free solution, whereas it decreased in a chloride-containing solution. The defect density in the substrate had no remarkable effect on passivation but the thickness of the passive film was slightly increased on twisted whiskers. The anodic polarization curve of a grown whisker in a chloride-containing solution did not exhibit a distinct pitting potential. By twisting of whisker, however, a current rise due to pitting appeared on the polarization curve and the apparent pitting potential shifted in the negative direction with increasing angle of twisting. Potentiostatic polarization experiments in a chloride-containing solution showed the emergence of random current pulses due to the breakdown of passive film and to repassivation. It is highly probable that the breakdown of the passive film occurs at the physical or chemical inhomogeneities in the passive film not associated with dislocation termini but that pitting occurs only when the breakdown occurs at emergent dislocation sites.     

316L不锈钢无铬钝化工艺研究

利用动电位扫描法和化学浸泡研究了316L不锈钢在两种无铬钝化工条件下所形成的钝化膜的耐点蚀性能,结果表明,钝化液组分Wb具有良好的钝化效果。     

DECREASING PITTING SUSCEPTIBILITY OF PASSIVE FILMS ON X70 PIPELINE STEEL IN NaCl SOLUTIONS BY ILLUMINATION

The influence of UV illumination on passivity and pitting susceptibility on X70 pipoeline steel in a borate buffer （pH=8.4 ） solution containing NaCl is described. It is observed that illumination of the sample leads to a decrease in its pitting susceptibility as indicated by pitting potential and incubation time measurements in chloride containing electrolytes. This effect is strongly dependent on the applied potential during passivation. The electronic properties of the passive films on X70 steel were studied by Mott-Schottky analysis and photocurrent transient measurements. The results indicated that illumination during passivation led to modifications in the electronic properties of the passive films, mainly to a decrease of the bulk doping and an increase in the surface state density. The cause for the decrease in the pitting susceptibility is preliminary explained in terms of such modifications of the passive flm.     

氢对纯铁钝化膜电子性质的影响

采用电化学、光电化学和交流阻抗等方法研究了氢对纯铁钝化膜形成过程和电子性质的影响。结果表明氢的存在会延长钝化膜的形成,增加稳态钝化条件下的溶解速率;氢能提高钝化膜光电流、降低禁带宽度;氢促使钝化膜的电容和掺杂浓度升高,并降低膜的平带电位。     

Improvement on the pitting corrosion resistance of 304 stainless steel via duplex passivation treatment

A remarkable improvement in the pitting corrosion resistance of 304 stainless steel was attempted using a novel duplex passivation treatment method. First, chemical passivation in nitric acid followed electrochemical passivation via potential polarization of step cycling in sodium nitrate electrolyte. Compared with traditional chemical passivation, breakdown potential was increased from 0.31 V_SCE to positive than 0.9 V_SCE at 70°C in a solution bearing 0.6 M [Cl^?] concentration. The critical pitting temperature was enhanced from 21.5°C to above 70°C in a solution with 6 M [Cl^?] concentration. Impedance analysis and X‐ray photoelectron spectroscopy results show that a more compact passive film with a higher ratio of chromium oxide on iron oxide was achieved by electrochemical passivation compared with chemical passivation. Morphology observation suggested that the potential polarization of step cycling slightly increased the dissolution of inclusions after being subjected to chemical passivation. The probable reason for the improvement on pitting resistance is discussed in detail based on inclusion dissolution and the protectiveness in passive film.     

模拟水中硫离子对不锈钢钝化膜破坏作用的光电化学研究

采用光电化学方法研究了模拟冷却水中硫离子对不锈钢钝化膜的破坏作用.结果表明,不锈钢钝化膜显示n-型光响应,最大吸收峰出现在310 nm处.不锈钢钝化膜在电位约-0.35 V开始出现光电流,随电位升高,光电流增大.钝化膜禁带宽度Eg随电位的升高而减小,并逐渐向铁氧化物的Eg靠近.模拟冷却水中加入硫离子使不锈钢钝化膜的光电流增大,Eg减小.硫离子的浓度越大,测得的光电流越大,而Eg越小,这可归因于钝化膜膜电阻的降低及钝化膜中氧化铬含量的减少.     

HCO3–对超级13Cr马氏体不锈钢钝化行为及点蚀行为的影响

目的研究在0.1 mol/L NaCl硼酸缓冲溶液中,研究HCO_3~–对超级13Cr马氏体不锈钢的钝化及点蚀行为的影响。方法采用动电位极化、恒电位极化、Mott-Schottky曲线、电化学阻抗谱等电化学测试手段,并结合3D超景深显微镜进行点蚀形貌观察,研究超级13Cr马氏体不锈钢的电化学腐蚀行为。结果随着HCO_3~–浓度的增加,超级13Cr的钝化区间变宽,点蚀电位向正向移动,稳态点蚀发生的敏感性降低。HCO_3~–减少了超级13Cr亚稳态点蚀数量,降低了亚稳态点蚀电流密度峰值的平均值。随着HCO_3~–浓度的增大,超级13Cr钝化膜电阻Rf升高,电荷转移电阻Rct升高,钝化膜电容Cf逐渐减小。HCO_3~–使得超级13Cr钝化膜半导体特性由n型转变为n+p型双极性,且随着溶液中HCO_3~–浓度的增大,钝化膜中的施主密度ND和受主密度NA减小。结论 HCO_3~–的加入使得超级13Cr不锈钢钝化膜厚度增大,钝化膜内点缺陷密度降低,对基体的保护作用增强,抑制了超级13Cr的亚稳态和稳态点蚀发生。     

利用动电位再活化法研究外加阴离子对铁钝化过程的影响

本文运用动电位再活化法研究了酸性溶液中阴离子对铁钝化过程的影响。在给定实验条件下,卤素离子对铁钝化膜的影响以Br~->Cl~-8>F~-、I~-的顺序递减;NO_3~-可以抑制Cl~-对阳极钝化区铁电极表面的孔蚀。扫描电镜实验得到相同结果。动电位再活化法是一种研究侵蚀性阴离子和抑制剂对金属钝化膜作用的快速而有效的方法。     

Cl~-对高氮不锈钢在0.5mol/L NaOH溶液中腐蚀行为的影响

利用动电位极化曲线、电化学阻抗谱和恒电位极化电流响应曲线对一种高氮不锈钢在含不同浓度Cl~-的0.5mol/L NaOH溶液中的腐蚀行为进行了研究。结果表明:高氮不锈钢在含Cl~-的0.5mol/L NaOH中具有良好的耐蚀性,极化曲线表现出阳极钝化特征,Cl~-浓度对点蚀电位无显著影响,钝化电流密度随Cl~-浓度的增加而增大;当Cl~-浓度增加到1.00mol/L时,高氮不锈钢表面生成的钝化膜呈n型半导体,仍具有良好的保护性,钝化膜的载流子密度随着Cl~-浓度的增加而增大。