Investigation of the deterioration of passive films in H<Subscript>2</Subscript>S-containing solutions

The effect of H₂S on the corrosion behavior of 316L stainless steel was investigated using electrochemical methods by changing the gas condition from CO₂ to H₂S and then back to CO₂. The presence of H₂S showed an acceleration effect on the corrosion of 316L stainless steel in comparison with CO₂. The acceleration effect remained even after the complete removal of H₂S by CO₂, indicating that the passive film was irreversibly damaged. X-ray photoelectron spectroscopy (XPS) analysis indicated that the passive film was composed of Cr₂O₃, Fe₂O₃, and FeS₂ after being immersed in H₂S-containing solutions. The semiconducting property of the passive film was then investigated by using the Mott-Schottky approach. The presence of sulfides resulted in higher acceptor and donor densities and thus was responsible for the deterioration of passive films.     

钝化预处理对316L不锈钢在漂液中电化学腐蚀性能的影响

采用电化学测试、SEM分析等方法,研究了316 L不锈钢在质量分数为30%的浓硝酸溶液及98%硫酸+20 g/L硝酸钾混合液两种钝化剂预处理后的特性,以及在ClO2漂液中的电化学抗腐蚀性能。结果表明,316 L不锈钢在25℃、30%硝酸介质中处理30 min时抗点蚀能力ΔE可达到773 mV,钝化效果较好。EIS图谱表明:316 L不锈钢在ClO2漂液中具有双容抗弧特征,钝化处理容抗弧半径较未钝化的增大,处理后的316 L不锈钢在60℃出现了Warburg阻抗;钝化膜的外层电阻和内层电阻均比未钝化的大。经钝化处理后的316 L不锈钢在ClO2漂液中的受腐蚀速率较未钝化的降低近一半,与钛材相比耐蚀性较差,但能在一定条件下起到减缓腐蚀的作用。     

316L和316LN不锈钢在高温高盐溶液中钝化膜的性能研究

利用电化学及扫描电子显微镜（SEM）对316L与316LN两种不锈钢在高温高盐环境中的耐蚀性能进行了对比研究,利用Mott-Schottky曲线研究了两种材料的钝化膜半导体特征,借助X射线光电子能谱（XPS）研究了316LN不锈钢的钝化膜结构以及N元素在钝化膜中的分布状态。结果表明：在高温高盐环境中,两种材料形成的钝化膜都为n型半导体;316LN不锈钢形成的钝化膜耐点蚀性能更好,其钝化膜内缺陷浓度更低,N元素会在钝化膜中富集。最后利用点缺陷原理对316LN钝化膜的耐蚀机理进行了研究。     

Study on pitting process of 316L stainless steel by means of staircase potential electrochemical impedance spectroscopy

Pitting corrosion of 316L stainless steel in NaCl solution was investigated by means of staircase potential electrochemical impedance spectroscopy (SPEIS). The investigation focused on the transition of stainless steel from the passive state to pitting corrosion. Based on the evolution of electrical parameters of the equivalent electrical circuit, it is suggested that the most probable mechanism of pit creation is the film breaking model. The result demonstrates that staircase potential electrochemical impedance spectroscopy is an effective method for the investigation of pitting corrosion.     

Properties of passive film formed on 316L/2205 stainless steel by Mott-Schottky theory and constant current polarization method

Semiconductor properties of the passive films formed on 316L and 2205 stainless steel were studied by Electrochemical Impedance Spectroscopy(EIS) in the high-temperature acetic acid.The results showed that the corrosion resistance of 2205 was higher than that of 316L,and the passive films formed on 316L and 2205 stainless steel showed p-type and n-type semiconductor behavior,respectively.Destruction and self-repairing of passive films were studied by using the constant current polarization method.The result...     

锌铝合金镀层表面低铬钝化膜的研究

探索了低浓度铬酸盐钝化处理在热浸镀锌铝合金镀层上的应用·采用盐雾试验、电化学腐蚀试验和人造海水浸泡试验对锌铝合金镀层表面低浓度铬酸盐钝化膜的耐蚀性进行了测试,并借助ＸＰＳ和ＡＥＳ对钝化膜的组成进行了分析·结果表明,锌铝合金镀层经低铬酸盐钝化处理后耐蚀性得到了显著提高,钝化膜的元素组成(原子数分数,％)为:Ｓ５－５,Ｎａ３－４,Ｃ１１－８,Ｔｉ７－９,Ｏ４１－６,Ｃｒ１３－７,Ｚｎ１６－０·     

409L和430铁素体不锈钢耐局部腐蚀性能

采用电化学测试技术与化学浸泡实验相结合,对比研究了409L和430铁素体不锈钢热轧板材耐点蚀和耐晶间腐蚀的能力.结果表明:409L不锈钢的击穿电位与保护电位的差小、钝化膜的修复能力较强,表现为小尺度的浅点蚀孔;430不锈钢的击穿电位较高,耐点蚀能力高于409L不锈钢,但430不锈钢热轧态的条带组织有明显的腐蚀微电池效应,表现为比较严重的全面腐蚀;409L不锈钢含Cr量低,且其热轧态未经过稳定化处理,使得409L不锈钢耐晶间腐蚀能力劣于430不锈钢.经微观分析:409L不锈钢为沿着基体等轴晶界的典型晶间腐蚀形貌特征,而430不锈钢在轧向碳化物(M23C6)与基体的相界面上呈现分层腐蚀痕迹.     

Passivity breakdown of 13Cr stainless steel under high chloride and CO_2 environment

Herein, the effect of high chloride ion(Cl~-) concentration on the corrosion behavior and passive film breakdown of 13Cr martensitic stainless steel under CO_2 environment was demonstrated. The Cl~- concentration was varied from 30 to 150 g/L and cyclic potentiodynamic polarization was conducted to investigate the influence of the Cl~- concentration on the corrosion potential(E_(corr)), passive breakdown potential(E_(pit)), and repassivation potential(E_(rep)). The results of the polarization curves revealed that 13Cr stainless steel is susceptible to pitting under high Cl~- concentration. The passive breakdown potential and repassivation potential decreased with the increase of Cl-concentration. The semiconducting behavior of the passive film was investigated by Mott-Schottky analysis and the point defect model(PDM). It was observed that the iron cation vacancies and oxygen vacancies were continuously generated by autocatalytic reactions and the higher Cl~- concentration resulted in higher vacancies in the passive film. Once the excess vacancies condensed at the metal/film interface, the passive film became locally detached from the metal, which led to the breakdown of the passive film.     

表面状态对核级316LN不锈钢电化学腐蚀行为的影响

表征了打磨态和机械抛光态316LN不锈钢表面的粗糙度、表面残余应变和表面电子功函数的分布,并研究了打磨态和机械抛光态样品在硼酸盐溶液中电化学腐蚀行为的差异.与机械抛光态316LN不锈钢相比,打磨处理后样品表面较为粗糙,且表面的微观残余应变较大,近表面产生约50 μm的加工硬化层.表面粗糙度和微观应变的增加引起打磨态表面电化学活性的增大,从而促进316LN不锈钢在硼酸盐溶液中腐蚀.机械抛光处理降低了表面钝化膜的载流子密度(供体和受体),并增大了钝化膜的阻抗,提高了钝化膜的致密性和保护性,能够有效抑制金属的进一步腐蚀.     

SO2-4对含Cl-溶液中316 L奥氏体不锈钢钝化行为及点蚀行为的影响

利用动电位极化、电化学阻抗、恒电位极化以及恒电流极化等电化学测试手段,并结合扫描电镜进行点蚀形态观察,探究了含Cl-溶液中SO2-4浓度对316L奥氏体不锈钢的钝化行为及点蚀行为的影响.结果表明,含Cl-溶液中SO2-4的加入能够使316L不锈钢钝化区变宽,使点蚀电位变正,维钝电流密度降低,进而提高316L的耐点蚀能力.但是在点蚀发生后,随着SO2-4浓度的升高,点蚀内部和边缘形态表现出更为复杂的趋势,蚀坑的周长面积比明显增大.     

Conductive and corrosion behaviors of silver-doped carbon-coated stainless steel as PEMFC bipolar plates

Ni–Cr enrichment on stainless steel SS316L resulting from chemical activation enabled the deposition of carbon by spraying a stable suspension of carbon nanoparticles; trace Ag was deposited in situ to prepare a thin continuous Ag-doped carbon film on a porous carbon-coated SS316L substrate. The corrosion resistance of this film in 0.5 mol·L-1 H₂SO₄ solution containing 5 ppm F- at 80℃ was investigated using polarization tests. The results showed that the surface treatment of the SS316L strongly affected the adhesion of the carbon coating to the stainless steel. Compared to the bare SS316L, the Ag-doped carbon-coated SS316L bipolar plate was remarkably more stable in both the anode and cathode environments of proton exchange membrane fuel cell (PEMFC) and the interface contact resistance between the specimen and Toray 060 carbon paper was reduced from 333.0 mΩ·cm2 to 21.6 mΩ·cm2 at a compaction pressure of 1.2 MPa.     

AISI316L奥氏体不锈钢在摸拟人体组织液中腐蚀疲劳裂纹萌生的初步研究

AISI316L奥氏体不锈钢是较常用的金属植入材料之一.但在临床应用中,由它制成的植入物特别是全髋关节,常因腐蚀疲劳破断而失效.本文对316L不锈钢在Hank’s溶液中的腐蚀疲劳裂纹萌生机理进行了初步研究.结果发现,在Hank’s溶液中,自然钝化的316L不锈钢在稳定钝化态下,裂纹的萌生是由交变应力引起的微观塑性变形和Hank’s溶液交互作用的结果;在有点蚀产生的非钝化态下,裂纹的萌生是点蚀和腐蚀疲劳相叠加的结果.316L不锈钢经离子氮化表面处理后,提高了在Hank’s溶液中的抗点蚀能力,但在外加腐蚀电位的苛刻条件下,困氮化层发生晶间腐蚀和脱落而加速了裂纹的萌生     

S135钢在含CO2聚合物钻井液中腐蚀研究

利用高温高压反应釜研究油田常用的四种S135钢在含CO2聚合物钻井液中腐蚀行为。结果表明,平均腐蚀速率随温度或CO2分压增大而先增大然后降低;随流速增大而升高。S135钢在动态液相中的平均腐蚀速率远大于动态气相,无论在液相还是气相S135钢平均腐蚀严重情况依次为S135（A）＞S135（B）＞S135（C）＞S135（D）。该实验条件下（温度为100℃,CO2分压为3MPa,流速为2m/s,腐蚀时间为96h）,S135钢气相局部腐蚀比较轻微,其点蚀系数介于1.12~1.49,液相局部腐蚀比较严重,其点蚀系数介于1.40~5.22。用聚合物钻井液钻遇高含CO2气层时,建议采用S135（D）钻杆,最好不用S135（A）或S135（B）钻杆。     

渗钛合金层对316L不锈钢晶间腐蚀性能的影响

采用等离子表面合金化技术在316L不锈钢表面进行渗钛处理,对渗层的结构及其晶间腐蚀性能进行了分析,结果表明,在温度为1000℃、保温时间为3.5h的渗钛条件下形成了表面改性合金层。在不锈钢10%草酸浸蚀试验中,316L不锈钢基体呈现七类凹坑组织Ⅱ晶间腐蚀;而渗钛合金层几乎没有发生晶间腐蚀,显著提高了316L不锈钢的耐晶间腐蚀性能。     

Comparative study on the corrosion behavior of X52, 3Cr,and 13Cr steel in an O2–H2O–CO2 system: products,reaction kinetics,and pitting sensitivity

The corrosionbehaviors of X52, 3Cr low-alloy steel, and 13Cr stainless steel were investigated inanO2–H2O–CO2 environment at varioustemperaturesand O2–CO2partial-pressure ratios. The results showed thatthe corrosion rates of X52, 3Cr, and 13Cr steels in-creased with increasing temperature. The corrosion ratesslowly increased at temperaturesless than100℃ and increased sharply when the temperature exceeded100℃. In the absence of O2, X52, 3Cr, and 13Cr exhibited uniform corrosion morphology and FeCO3 was the main corrosion product. When O2 was introduced into the system, various forms of Fe2O3 appeared on the surface of the samples. The Cr content strongly influenced the corrosion resistance. The 3Cr steel with a low Cr content was more sensitive to pitting than the X52 or 13Cr steel. Thus, pitting occurred on the surface of 3Cr when 1.25 MPa of O2 was added; this phenomenon is related to the non-uniform distribution of Cr in 3Cr.     

Flow-accelerated corrosion behavior of 13Cr stainless steel in a wet gas environment containing CO<Subscript>2</Subscript>

This work investigated the flow-accelerated corrosion (FAC) behavior of 13Cr in a wet CO₂-containing environment at different flowing gas velocities and impinging angles, with the natural-gas pipeline environment simulated by a self-assembled impingement jet system. Surface morphology determination, electrochemical measurements, and hydromechanics numerical analysis were carried out to study the FAC behavior. The results demonstrate that pitting corrosion was the primary mode of corrosion in 13Cr stainless steel. High-flow-rate gas destroyed the passive film and decreased the pitting potential, resulting in more serious corrosion. The corrosion degree with various impact angles showed the following order: 90° > 60° > 45°. The shear force and the electrolyte from the flowing gas were concluded to be the determinant factors of FAC, whereas the shear force was the main factor responsible for destroying the passive film.     

镁合金在大气环境中的电偶腐蚀

研究了AZ91D,AM50,AM60三种镁合金分别与Q235碳钢、316L不锈钢、H62黄铜、LY12铝合金4种材料组成电偶对在青岛和武汉大气暴晒实验场进行周期分别为3,6,15,20,27个月的大气腐蚀行为及规律. 结果表明,镁合金作为电偶对的阳极其腐蚀速率在与实验所用材料偶接后显著提升. 其中,与Q235碳钢、316L不锈钢偶接后大气电偶腐蚀效应最大,而与LY12铝合金偶接后大气电偶腐蚀效应最小. 青岛站镁合金试样的大气电偶腐蚀效应要明显高于武汉站的试样. 不同镁合金的大气电偶腐蚀效应γ之间存在的基本关系为AZ91D最大,AM50最小.     

超级13Cr马氏体不锈钢在CO_2 及H_2 S/CO_2 环境中的腐蚀行为

在模拟油田腐蚀环境中,通过高温、高压、CO2和H2S/CO2腐蚀实验及电化学测试,研究超级13Cr马氏体不锈钢的腐蚀行为.结果表明:在CO2腐蚀环境中,随着温度的升高,超级13Cr的均匀腐蚀速率呈稍微上升的趋势,点蚀轻微;在H2S、CO2共存条件下,超级13Cr的均匀腐蚀速率变化不大,点蚀严重,当Cl-的质量浓度为160g.L-1时,其最大点蚀深度可达28μm.超级13Cr的点蚀电位明显高于普通13Cr的点蚀电位,温度升高、Cl-的质量浓度增大和H2S气体的存在降低了超级13Cr的点蚀电位,而CO2对超级13Cr的点蚀电位影响不大;在N2、CO2环境中,超级13Cr的回复电位都在钝化区间,且回复电位较高,具有良好的再钝化能力.H2S气体的存在同样使超级13Cr的回复电位和点蚀电位显著降低.     

液固流动相中不锈钢耐颗粒冲刷腐蚀性能研究

采用自制的旋转冲刷腐蚀失重装置，研究了湿法磷酸中固体颗粒的性质，如固含量，粒径等环境参数对不锈钢316L和904L冲刷腐蚀速率的影响，并在扫描电镜下观察了不锈钢腐蚀的形貌，试验结果表明，CaSO4结晶颗粒固含量质量分数由10％增加到50％时，冲刷腐蚀速率有所增大，316L不锈钢主要以腐蚀为主，且表现为晶间腐蚀，当浆体中含有SiO2固体颗粒时，液相腐蚀性得到降低，虽然不锈钢904L耐液相腐蚀性能优良，但耐冲刷（磨损）性能较差，尤其当SiO2粒径增大时，冲刷腐蚀速率明显增大。     

316L不锈钢应力腐蚀研究进展

316L不锈钢具备良好的力学性能、焊接性能、耐蚀性能，被广泛应用于化工管道、船舶及核电等领域。因其应用环境复杂，316L不锈钢在特定介质环境和拉应力的协同作用下，易发生应力腐蚀开裂，导致严重事故。概述了316L不锈钢应力腐蚀裂纹萌生及扩展的规律，总结了其应力腐蚀的阳极溶解和氢致开裂两种微观主导机制的特点。在此基础上，针对介质环境、材料、表面应力状态3个影响因素，综述了近年来通过调节介质环境的pH、溶液浓度、引入压应力、优化微观结构及涂层工艺等方面，改善316L不锈钢应力腐蚀性能的研究进展。最后，基于316L不锈钢面临的应力腐蚀问题，从应力腐蚀机制和防护措施两方面展望了316L不锈钢应力腐蚀的研究热点和方向。