Fe基合金钝化膜点蚀敏感性的电化学研究

应用电位扫描、交流阻抗、电化学噪声等方法研究Fe及其合金在中性水溶液中钝化膜的形成过程、电子性质和点蚀敏感性以及不同微组织结构间的相互作用.结果表明:由Mott-Schot tky关系式确定钝化膜的电子性质仅限于较窄的低电位范围;在较高电位下,电容倒数与电位的线性关系当归因于钝化膜厚度的变化;反映钝化膜缺陷的电子性质与合金的点蚀敏感性有关,钝化膜电子供给体浓度越高,点蚀倾向越强。钝化膜的电子性质受钝化膜形成电位、钝化剂种类以及合金的微组织结构影响;不同微组织结构之间存在相互作用,这种相互作用能够诱导缺陷较大的一方发生点蚀。铁素体与珠光体和/或马素体相互作用时,点蚀在铁素体形成和发展.     

Characterization of the Passive Film and Corrosion of Martensitic AM355 Stainless Steel

Electrochemistry methods were used to investigate the influence of pH on the passive film and corrosion behavior of ultrahigh strength AM355 stainless steel in chloride-containing media. Analysis of the Pourbaix diagram indicates that AM355 stainless steel exhibits higher corrosion resistance in natural and near-natural environments than that in acidic and alkaline conditions. Electrochemistry measurements and composition analysis of the passive film show that pitting potential increased due to the enhanced repassivation capacity of AM355 stainless steel with increasing pH. The mixed MnS/oxide inclusions are the main pitting sensitive locations under all conditions. Morphological observations and energy-dispersive spectroscopy showed that the influence of the gap between the martensitic laths is significant with increasing pH. The inclusions, element concentrations, and microstructures weaken the resistance of ultrahigh-strength martensitic AM355 stainless steel against corrosion.     

Study on the Corrosion Resistance of 304L Stainless Steel

304L is an austenitic stainless steel with very low carbon content, and is served as the application to the oxidizing media, however, its corrosion resistance is not satisfactory in reducing media. For example, the pitting corrosion occurred on 304L stainless steel tube, which had been mounted for one year, somewhere at the power station in die seashore of China. For this reason we have studied the corrosion behavior of 304L in some media and invented a novel surface treatment technique of stainless steel for extremely improving the corrosion resistance of 304L. The characteristics of the modified passive film on the steel were examined in this paper, and the corrosion resistance of treated 304L stainless steel was tested in our laboratory and the testing ground. The results are satisfactory.     

高温高浓度溴化锂溶液对低合金钢的电化学行为作用

通过电化学测式技术和化学浸泡方法 ,在高温 55%LiBr +0 .0 7mol/LLiOH溶液中研究了MoO4 2 - 对低合金钢的电化学行为作用 .结果表明 ,MoO4 2 - 作为阳极型缓蚀剂能促进钝化 ,阻滞了阳极和阴极反应 .Na2 MoO4 浓度达到 2 0 0mg/L时 ,可有效地抑制低合金钢的活性溶解 .低合金钢中添加Cr和Ni元素可改善耐蚀性能 ,而AI元素则使耐蚀性能变劣 .Mo元素参与成膜过程 ,Cr和Mo元素的协调作用 ,使A钢能在较低Na2 MoO4 浓度下进入钝态     

抗菌处理含铜铁素体不锈钢的耐微生物腐蚀性能

采用电化学测试技术及微生物学方法, 研究了抗菌处理含铜铁素体不锈钢在含有培养基的异养菌溶液中的耐蚀性能. 结果表明, 不锈钢的腐蚀电位随异养菌的新陈代谢呈现规律性变化, 抗菌处理使不锈钢在菌液中钝化膜的稳定性得到改善, 点蚀敏感性降低; 抗菌不锈钢表面弥散分布的ε-Cu析出相的杀菌作用, 降低了异养菌的活性, 减缓了异养菌对抗菌不锈钢的腐蚀, 提高了抗菌不锈钢耐微生物腐蚀性能.     

铬对碳钢在NaHCO3/NaCO3缓冲溶液中所成钝化膜半导体性能的影响

应用电化学阻抗谱技术研究铬对碳钢钝化膜半导体性能的影响.实验表明,在碳酸氢钠/碳酸钠缓冲溶液中碳钢形成的钝化膜具n型半导体特性,而含有3%铬的碳钢钝化膜则呈n-p型半导体特性,随着成膜电位的增加,以上两种钝化膜之Mott-Schottky直线部分的斜率均呈增大的趋势,表明成膜电位升高,膜内的杂质密度减小,但铬的加入使得碳钢钝化膜的施主密度增加约一个数量级,从而增加了碳钢点蚀发生的趋势.EIS分析表明:铬的加入降低了钝化膜的传递电阻R1和膜电阻R2,特别是膜电阻R2下降达3个数量级,这就有可能增加碳钢在高pH值环境中的腐蚀.     

不锈钢点腐蚀发生的早期过程 Ⅰ. 扫描微参比电极法研究

本文应用扫描微参比电极联机测量系统对18-8型不锈钢在含Cl~-介质中点腐蚀发生的早期过程进行研究。结果表明, 在点腐蚀发生的早期阶段, 可用特征电位E_r表征表面钝化膜的局部破坏和微点腐蚀的发生, E_r电位与传统的E_P电位不同, E_r电位通常比E_p, 电位更负100—400 mV, E_r电位值与钝化膜的表面状态直接有关, 且随介质Cl~-浓度的增加和pH的降低而负移。在E_r电位附近, 微点腐蚀开始发生, 但一般不能稳定发展, 电位越接近于E_p, 则已发生的微点腐蚀越容易扩展为宏观点腐蚀, 由此, 作者提出“不稳定微点腐蚀”的新概念, 并对不锈钢点腐蚀发生的早期过程机理加以讨论。     

Pitting of Al and Al–Si alloys in KSCN solutions and the effect of light

The pitting corrosion susceptibility of pure Al and three Al-Si alloys, namely (Al-6%Si), (Al-12%Si) and (Al-18%Si) has been studied in 0.04 M KSCN solution. Measurements were carried out under the effect of various experimental conditions using cyclic polarization, potentiostatic and galvanostatic techniques. In all cases, the potentiodynamic anodic polarization curves do not exhibit active dissolution region due to spontaneous passivation. The passivity is due to the presence of a thin film of Al₂O₃ on the anode surface. The passive region is followed by pitting corrosion, at a certain critical potential, pitting potential (E_pit), as a result of breakdown of the passive film by SCN^? anions. Cyclic polarization measurements allowed the determination of the pitting corrosion parameters, namely the pitting potential and the repassivation potential (E_rp). Alloyed Si decreased the passive current (j_pass) and shifted both E_pit and E_rp towards more positive values. Thus alloyed Si suppressed pitting attack. The effect of illumination on passivity and the initiation of pitting corrosion on Al in KSCN solutions was also studied. It is observed that illumination of Al leads to an increase in its pitting corrosion resistance-apparent from j_pass, E_pit, and E_rp measurements in aggressive KSCN solutions.     

XPS and AES analysis of passive films on Fe-25Cr-X (X = Mo, V, Si and Nb) model alloys

Corrosion resistance of stainless steel is due to the presence of a thin passive film of typically 1–2 nm thickness. The influence of ternary alloying elements on the composition of passive films on Fe-Cr alloys and their pitting corrosion resistance has been investigated. Iron-chromium alloys were analyzed by XPS and AES with model alloys (Fe-25Cr-X with X = at % Mo, Si, V and Nb) formed in sulphate solution in the presence and absence of chloride ions. All ternary alloying elements increase the pitting potential compared to the corresponding binary alloy. Films formed in chloride containing sulphate solution contain both electrolyte anions. Scanning Auger microscopy reveals that for a two phase system such as Fe-25Cr-11Nb, the dendritic phase is enriched with chromium, while essentially all of the niobium is located in the interdendritic eutectic.     

XPS and AES analysis of passive films on Fe-25Cr-X (X = Mo,V, Si and Nb) model alloys

Corrosion resistance of stainless steel is due to the presence of a thin passive film of typically 1-2 nm thickness. The influence of ternary alloying elements on the composition of passive films on Fe-Cr alloys and their pitting corrosion resistance has been investigated. Iron-chromium alloys were analyzed by XPS and AES with model alloys (Fe-25Cr-X with X = at % Mo, Si, V and Nb) formed in sulphate solution in the presence and absence of chloride ions. All ternary alloying elements increase the pitting potential compared to the corresponding binary alloy. Films formed in chloride containing sulphate solution contain both electrolyte anions. Scanning Auger microscopy reveals that for a two phase system such as Fe-25Cr-11Nb, the dendritic phase is enriched with chromium, while essentially all of the niobium is located in the interdendritic eutectic.     

不锈钢钝化膜耐蚀性与半导体特性的关联研究

通过极化曲线、交流阻抗谱和钝化膜半导体特性等电化学测量，研究了经电化学阳极氧化处理的不锈钢钝化膜在0.5 mol•L^-1 NaCl溶液中耐蚀性能与其半导体特性的关系，进一步探索电化学改性处理不锈钢钝化膜的耐蚀机理. 结果表明，不锈钢钝化膜在负于平带电位范围表现为p型半导体，在高于平带电位范围表现为n型半导体，这主要与组成钝化膜的Fe和Cr氧化物半导体性质有关. 与自然条件下形成的不锈钢钝化膜比较，发现经过电化学阳极氧化后不锈钢钝化膜具有较低的施主与受主浓度，平带电位负移，说明阴离子在钝化膜表面发生吸附. 低的施主与受主浓度及钝化膜表面负电荷的增强，可有效排斥侵蚀性Cl^－在钝化膜表面的特性吸附，有利于提高不锈钢的耐局部腐蚀性能.     

Monitoring of titanium base alloys-biofluids interface

Monitoring of the titanium, Ti-5Al-4V, Ti-6Al-4Fe implant materials--Ringer 1 and Ringer 2 solutions (of different pH values) interface for long term was studied in this work. In Ringer 1 solution (with high chloride ion content) all biomaterials present self-passivation. On Ti-6Al-4Fe alloy, the breakdown of the passive film was registered but at high pitting potential; pitting protection potential is very noble and can not be reached in human fluids. In Ringer 2 solution was obtained more electropositive corrosion potential values than in Ringer 1 solution; pitting corrosion of Ti-6Al-4Fe alloy is characterised by nobler breakdown and pitting protection potential values, therefore a better pitting corrosion resistance and tendency. Ion release increases in time, for the first 400-600 immersion hours and then tend to a constant level with very low values, non-dangerous for human body. All open circuit potentials oscillate around some electropositive values. The potential gradients calculated for extreme pH values have low values during 20,000 exposure hours and can not accelerate the corrosion. Atomic Force Microscopy images obtained after different exposure periods in Ringer 1 solution revealed that the roughness increased in time, suggesting a dynamic process at biomaterial-biofluid interface. X-ray Photoelectron spectra obtained after 2880 immersion hours in Ringer 2 solution show the existence of protective titanium dioxide TiO(2) and TiO and Ti(2)O(3) oxides both for titanium and Ti-5Al-4V alloy. Also, Al(2)O(3) oxide was detected.     

Corrosion resistances of passive films on low‐Cr steel and carbon steel in simulated concrete pore solution

The passive ranges of carbon steel rebar and 3Cr steel rebar in saturated Ca(OH)₂‐simulated concrete pore solution with pH 12.6 were determined by means of cyclic voltammetry and potentiodynamic polarization curves. Chronopotentiometry was used to obtain steady‐state conditions for the formation of passive films on rebar samples at different anodic potentials. Electrochemical impedance spectroscopy, Mott–Schottky and X‐ray photoelectron spectrometer curves were employed to compare the formed passive films at different potentials. Additionally, cyclic polarization curves were used to compare the corrosion resistances of formed passive films on the two rebars in saturated Ca(OH)₂‐simulated concrete pore solution with different concentration of Cl^?. The results show that the passive ranges of the two rebars are all between ?0.15 and +0.6 V, and more stable passive films can be formed on both rebars at the anodic potential of +0.3 V. In the absence of Cl^?, the stability and corrosion resistance of the passive film formed on the 3Cr rebar are better than those of CS rebar. The passive film of 3Cr steel has the relatively better pitting corrosion resistance than carbon steel in saturated Ca(OH)₂‐simulated concrete pore solution that contains different concentration of Cl^?. Copyright © 2016 John Wiley & Sons, Ltd.     

实用电极材料体系的共焦显微拉曼光谱研究(英文)

本文简要介绍了实验室内有关利用共焦显微拉曼光谱于某些实用电极材料 (表面 )性能研究的结果 .具体的研究实例包括 :尖晶石锂锰氧化物中Li+ 的嵌入 脱出过程 ,AB5 型金属氢化物电极表面氧化物的性能和钢筋电极表面钝化膜及其孔蚀过程 .     

钽在无水乙醇中的腐蚀

采用动电位极化、循环伏安、交流阻抗和扫描电镜等技术研究了钽在四乙基氯化铵（TEA）乙醇溶液中的腐蚀行为．在循环伏安曲线的扫描初期,电极表面因存在一薄层氧化物膜而使得电流密度缓慢增加．后来钝化膜因受到氯离子的攻击而被击穿,即点蚀．扫描电镜图很好地显示出蚀孔的生长过程．点蚀电位随着TEA浓度的增加而下降,随着水含量的增加而上升．在所研究的温度范围内,电化学反应的活化能为36kJ／mol．所有电极电位下的交流阻抗图谱都包含两个时间常数,钝化膜电阻和电荷传递电阻均随电极电位的增加而下降．     

合金元素及模拟热处理对2205双相不锈钢之孔蚀性质影响

本文研究了Ｎｉ元素及不同模拟焊后热影响区（ＨＡＺ）组织对２２０５双相不锈钢孔蚀性质之影响。结果发现：在研究成分范围内，不同Ｎｉ含量对于底材电化学极化曲线之影响不大，其Ｅｎｐ和Ｅｎｐ均在１１００￣１２００ｍＶ之间。     

钝化与过钝化状态下304不锈钢的点蚀行为研究

为了进一步了解不锈钢钝化膜与过钝化膜的性质,本文对比研究了在不同电位下极化处理后304不锈钢样品的点蚀及表面膜性质,发现空白对照组样品的点蚀电位和1.1 V过钝化处理后样品的点蚀电位相近,而0.5 V钝化处理后样品的点蚀电位较高. 扫描Kelvin探针（SKP）实验结果也验证了这一现象. 扫描电子显微镜（SEM）结果显示,空白对照组样品表面只呈现一般样品抛光后形貌;0.5 V钝化处理后的样品表面被颗粒状钝化膜所覆盖,该膜层决定了样品具有较好的耐蚀性;而1.1 V过钝化处理后的样品表面出现裂缝,导致不锈钢基体继续发生严重的局部腐蚀,可能成为过钝化膜保护性变差的主要原因.     

5083铝合金在海水中的腐蚀电化学行为及活性氯影响研究

采用动电位极化、循环极化和全浸腐蚀试验方法,研究了5083铝合金在静止海水中的腐蚀电化学性能以及活性氯的影响.结果表明,在本文设置的防污活性氯浓度范围(0.2～0.5mg/L)内,活性氯对铝合金的阴极和阳极电化学极化以及腐蚀行为没有明显影响,并可提高铝合金的耐点蚀能力,海水的pH值对铝合金的腐蚀具有显著的影响.该研究为海水中5083铝合金的防腐防污提供了依据.     

The effect of passivated potential on the passive films formed on pure chromium in borate buffer solution

The effect of passivated potential on corrosion resistance of the chromium in borate buffer solution was investigated. The electrochemical results showed that corrosion resistance of the passive film on the chromium electrode decreased with the increasing of passivated potential. The Mott–Schottky analysis showed that more acceptor concentrations in passive film due to higher passivated potential deteriorated corrosion resistance of the chromium electrode. The results from XPS showed that more chromium hydroxides were formed in higher passivated potential, while less chromium oxides were formed. More acceptor concentrations in passive films reduced corrosion resistance of the chromium electrode in borate buffer solution. Copyright © 2016 John Wiley & Sons, Ltd.     

Medicago sativa as a green corrosion inhibitor for 1018 carbon steel in 0.5 M H2SO4 solution

A study on the use of the methanol extract of Medicago sativa as a green corrosion inhibitor for 1018 carbon steel in 0.5?M of sulfuric acid has been carried out by using potentiodynamic polarization curves, electrochemical impedance spectroscopy and gravimetric tests. Testing temperatures were 25°C, 40°C and 60°C. Results showed that M. sativa is a good corrosion inhibitor, with its efficiency increasing with its concentration and with time, but decreasing with the temperature. M. sativa forms a passive film on top of the steel with a passive current density and pitting potential values lower than that for uninhibited solution, and remained on the steel for 8–12?h. This film formed by iron ions and heteroatoms present in OH^? and amine groups from the extract are adsorbed on the steel and form a protective film on to the steel.