Enhancement of corrosion resistance of a biomedical grade 316LVM stainless steel by potentiodynamic cyclic polarization

The paper discusses the results on the use of a simple cyclic linear potentiodynamic polarization technique as a method of improving corrosion properties of passive oxide films formed on a biomedical-grade 316LVM stainless steel surface in phosphate buffer. The results demonstrate that the modification of 316LVM surface by cyclic potentiodynamic polarization between the potential of hydrogen and oxygen evolution results in the formation of a passive film that offers significantly increased corrosion resistance (both pitting and general) when compared to the naturally grown passive film. The effect of number of cycles and anodic potential limit on the resulting corrosion properties is discussed. The capacitance analysis demonstrates that the major difference between the electrochemically formed and naturally grown passive film is in the type of semiconductivity in the potential region where pitting on the unmodified surface occurs. The XPS analysis shows that this is due to the presence of Cr(VI)-species in the electrochemically formed passive film, which contribute to the increased density of metal vacancies, and thus to the increased pitting corrosion resistance of the passive film.     

高氮奥氏体不锈钢耐点蚀性能研究

目前产于高氮不锈钢的研究多集中于理论基础、制造工艺和力学性能等方面,有关耐蚀性方面的研究有限。通过循环极化、Mott-Schottky曲线以及电化学阻抗(EIS)等方法,研究了Cr23Mo1N奥氏体不锈钢(高氮钢,HNSS)和316L不锈钢在Cl-溶液中的耐点蚀性能。结果表明:与316L不锈钢相比,高氮钢具有更正的自腐蚀电位,更小的维钝电流密度。阻抗谱表明高氮钢的钝化膜比316L更加稳定,且电荷转移电阻更大。Mott-Schottky曲线表明高氮钢的点缺陷施主浓度比316L不锈钢低一个数量级,钝化膜的绝缘性更好。循环极化曲线表明高氮钢的点蚀敏感性更小,钝化膜的自修复能力更强,耐蚀性能更加优越。     

不同Cr含量的Ni基合金电化学腐蚀行为

利用电化学测试技术研究不同Cr含量的Ni基合金耐Cl-离子水溶液腐蚀的能力。结果表明：Ni基合金耐Cr离子腐蚀性能随着合金中Cr含量的提高而增强,溶液中Cl-离子浓度对Ni-9Cr、Ni-15Cr和Ni-20Cr合金有较大影响,特别是Ni-9Cr合金在0．6mol／LNaCl溶液中腐蚀最为严重,而对于Ni-25Cr和N...     

Chemical composition and corrosion resistance of passive chromate films formed on stainless steels 316 L and 1.4301

The chemical composition and corrosion behavior of the natural and formed by chemical treatment in chromium-containing solution passive films on 316 L and 1.4301 stainless steel surfaces have been investigated by means of X-ray photoelectron spectroscopy and electrochemical in situ method of anodic polarization curves. It have been established that the oxide films formed by the chemical treatment have different chemical composition (Cr-enriched), color and reduced corrosion resistance compared to the natural passive films on both steels. The results have shown that the lower part of the oxide layer represents a uniform modified passive film and the upper one is a porous Cr³⁺-enriched film with an island-like structure. The latter permits a direct contact of the solution with the modified passive film which controls the corrosion resistance by the dissolution of the Fe³⁺ oxides present in the lower thinner layer.     

铁氧化菌作用下316L不锈钢点蚀电化学特性的研究

采用电化学测量、交流阻抗技术、扫描电镜观察和能谱分析等实验方法,研究了316L不锈钢在铁氧化菌(IOB)溶液中的腐蚀电化学行为,分析了炼油厂冷却水系统微生物腐蚀的特征及机制,结果表明,在含有IOB溶液中的自腐蚀电位(Ecorr)、点蚀电位(Epit)和极化电阻(Rp)均随浸泡时间的增加呈现出降-升-降的变化趋势;在含有IOB溶液中的腐蚀速率均大于在无菌溶液中;IOB的生长代谢活动及其生物膜的完整性和致密性影响了316L不锈钢表面的腐蚀过程,使不锈钢表面的钝化膜层腐蚀破坏程度增加,加速了316L不锈钢的点蚀.     

The effect of surface roughness on the efficiency of the cyclic potentiodynamic passivation (CPP) method in the improvement of general and pitting corrosion resistance of 316LVM stainless steel

The influence of surface roughness on the efficiency of a cyclic potentiodynamic passivation (CPP) method employed to increase the general and pitting corrosion resistance of 316LVM stainless steel was investigated. The results show that a decrease in surface roughness of both the surface on which the passive film was formed naturally and by the CPP method, results in an increase in general corrosion resistance of the material, while for the CPP-modified surface, a notable increase in pitting corrosion resistance was also observed. It was further demonstrated that the CPP method is highly effective in increasing the general and pitting corrosion resistance of 316LVM, and that its efficiency does not depend on the surface roughness.     

Pitting corrosion of 2Cr13 stainless steel in deep-sea environment

Pitting corrosion of 2Cr13 stainless steel was investigated by deep-sea exposure test at various depths of 500 m,800 m and 1200 m in the South China Sea for 4 months.With the aid of electrochemical measurements in simulated deep-sea environments and grey relational analysis,the influence of deepsea environments on passive film and the mechanism of pitting corrosion were discussed.The results indicated that with the increase of sea depth,pitting depth of 2Cr13 stainless steel increased,which can be attributed to the change of chemical composition and the degradation of pitting resistance of passive film.Film growth was greatly retarded in the condition of low seawater temperature and low dissolved oxygen content of deep sea,resulting in an unstable and vulnerable film.Pitting depth was most influenced by hydrostatic pressure,which can increase the adsorption and penetration of Cl-ion,and promote the proliferation of point defects in passive film,leading to rapid deconstruction of protective oxides of the film.Pitting sensitivity of 2Cr13 stainless steel increased eventually with the combination of accelerated dissolution and suppressed self-healing of passive film in deep sea.     

Pitting initiation of 316L stainless steel in the media of sulfate-reducing and iron-oxidizing bacteria

Pitting corrosion behavior of stainless steel 316L in the presence of aerobic and anaerobic bacteria isolated from cooling water system in oil refinery was investigated using open circuit potential measurement, electrochemically impedance spectroscopy, scanning electron microscopy examinations, and energy dispersive spectrum analysis. The results show the corrosion potential (E _cor) and polarization resistance (R _p) decrease in the presence of sulfate-reducing bacteria (SRB), iron-oxidizing bacteria (IOB), and a combination of SRB and IOB, in comparison with those observed in the sterile medium for the same exposure time. The presence of SRB demonstrated higher corrosion rates than IOB. The combination of SRB and IOB created the highest corrosion rate. The metabolic activity of bacteria and the integrality and compactness of biofilm influenced the pitting corrosion process, increased the corrosion damage degree of the passive film, and accelerated the pitting corrosion. It is suggested that SRB and IOB in influencing the pitting corrosion of 316L SS is highlighted. The text was submitted by the authors in English.     

铸造双相不锈钢点腐蚀行为研究

采用化学浸泡腐蚀试验及微观组织和化学成分分析研究了5种铸造双相不锈钢在6%Fe Cl3溶液中的点腐蚀行为,并与316L奥氏体不锈钢进行了对比。结果表明,铸造双相不锈钢的抗点腐蚀性能均优于316L的,腐蚀速率和点腐蚀深度均小于316L奥氏体不锈钢的;双相不锈钢主要耐点蚀能力合金元素在奥氏体和铁素体相内分布不均匀,铬、钼更多地分配于铁素体相内,而镍、氮则更多地分配于奥氏体相内,铁素体相的耐点蚀指数PRE(Cr%+3.3Mo%+16N%)大于奥氏体相;双相不锈钢的耐点腐蚀性能与化学成分有关,随着PRE的增加,双相不锈钢的耐点腐蚀性能提高,铜元素在铁素体内析出的富铜相导致点蚀优先在铁素体内发生和发展。     

AES study of passive films formed on a type 316 austenitic stainless-steels in a stress field

The type AISI 316 stainless steel, in addition to the principal alloying elements chromium and nickel, contains 2.5–3.5% of molybdenum. This element is added to improve the mechanical properties and the pitting resistance of austenitic alloys. Concerning the Stress Corrosion Cracking (SCC) resistance of austenitic stainless steels, molybdenum additions to alloys have a variable effect: the effect is detrimental for small additions of Mo, and it is beneficial for the alloy containing more than 4% Mo. Thus the Mo concentration on passive film plays an important role on the SCC resistance of steels. On the other hand, in a previous investigation, it was shown that the composition of passive films formed on the stressed 302 alloy depended on the compressive or tensile nature of stresses. Consequently, the aim of the present work is to study the composition of passive films formed on 316 steel and the migration of molybdenum in a stress field. Thus, Auger electron spectroscopy spectra were recorded to determine the chemical composition of the passive films formed on both sides of the type AISI 316 stainless steel U-bend samples. The results obtained show that the behaviour of chromium and oxygen in passive films formed on 316 steel in the stress field was nearly similar to that formed on 302 steel. Concerning the molybdenum diffusion outwards the passive film formed on the 316 steel was reduced by either the tensile or compressive stress field.     

Electrochemical characterization of metastable pitting of 3003 aluminum alloy in ethylene glycol–water solution

The corrosion and electrochemical behavior of 3003 aluminum alloy in ethylene glycol–water solution were investigated by electrochemical techniques. It is found that the oxide film formed on aluminum depends on the dissolved oxygen in the solution. In the presence of oxygen, a layer of aluminum oxide film forms on the aluminum surface to protect the substrate from corrosion. In the absence of oxygen, the film formed is mainly aluminum-alcohol film that is less compact and less resistant to corrosion. The aluminum oxide film and aluminum-alcohol film have the different susceptibilities to chloride ion attack for pit initiation. There is a higher pitting susceptibility for aluminum oxide-covered electrode. The increase in temperature decreases the resistance of aluminum electrode to corrosion reaction. However, the resistance to pitting corrosion increases.     

Electrochemical properties of 316L stainless steel with culturing L929 fibroblasts.

Potentiodynamic polarization and impedance tests were carried out on 316L stainless steel with culturing murine fibroblast L929 cells to elucidate the corrosion behaviour of 316L steel with L929 cells and to understand the electrochemical interface between 316L steel and cells, respectively. Potential step test was carried out on 316L steel with type I collagen coating and culturing L929 cells to compare the effects of collagen and L929 cells. The open-circuit potential of 316L steel slightly shifted in a negative manner and passive current density increased with cells, indicating a decrease in the protective ability of passive oxide film. The pitting potential decreased with cells, indicating a decrease in the pitting corrosion resistance. In addition, a decrease in diffusivity at the interface was indicated from the decrease in the cathodic current density and the increase in the diffusion resistance parameter in the impedance test. The anodic peak current in the potential step test decreased with cells and collagen. Consequently, the corrosion resistance of 316L steel decreases with L929 cells. In addition, collagen coating would provide an environment for anodic reaction similar to that with culturing cells.     

Microstructure and electrochemical behavior of laser treated Fe---Cr and Fe---Cr---Si---N surface alloyed layers on carbon steel

Laser surface alloyed Fe---Cr and Fe---Cr---Si---N layers on carbon steel were produced by laser irradiation involving preplaced Fe/Cr and Fe/Cr/Si₃N₄ powders, respectively. The effects of Cr content (13–25 wt.%) and microstructure on the corrosion behavior of the laser treated Fe---Cr and Fe---Cr---Si---N alloys in deaerated neutral 3.5 wt.% NaCl solution were studied. Potentiodynamic polarization tests and electrochemical impedance spectroscopy measurements were used to evaluate the corrosion resistance of the surface layers. The results showed that the Fe---Cr---Si---N treated layer with a fine duplex phase microstructure had a higher pitting potential than the Fe---Cr treated layers. The passive film resistances increased and the passive current density decreased with increasing Cr content in the Fe---Cr layer.     

Pitting corrosion inhibition of 316 stainless steel in phosphoric acid-chloride solutions Part II AES investigation

The application of Auger Electron Spectroscopy (AES) to the study of the composition and thickness of the passive film formed on the surface of 316 Stainless steel in H3PO4-Cl– solutions containing nitrate, dichromate, molybdate and tungstate as inhibitors is discussed. Data are presented which explain the effectiveness of the additives on the properties of the passive films of the alloy. It is concluded that much higher corrosion resistance of the alloy is observed in nitrate additives due to marked nitrogen enrichment underneath the passive film which enhances the repassivation ability of this alloy. The results could also explain the effectiveness of the dichromate, molybdate and tungstate anions due to improved film repair conditions.     

Effect of chromium on the corrosion behavior of iron aluminides in thiosulfate-chloride solution

Aqueous corrosion characteristics of iron aluminides in thiosulfate-chloride solution were studied as a function of chromium addition. Four kinds of iron aluminides, namely, FA-61, FA-77, FA-72 and FA-78, were prepared by arc melting followed by thermomechanical treatment. The corrosion behavior in thiosulfate-chloride solution for the prepared alloys were investigated by electrochemical tests (potentiodynamic test, potentiostatic test and electrochemical impedance spectroscopy (EIS) measurement) and surface analyses. The results of the potentiodynamic test indicated that the breakdown potential increased with increasing Cr content. Cr additions were found to prevent passive film from undergoing pitting corrosion. In EIS measurement, the depression angle was inversely related to pitting resistance, and decreased with increasing chromium content. The SEM observations of the sample surfaces reveal the different forms of pit as a function of chromium content. The AES results give evidence that the thiosulfate ions are reduced on the metallic surface, which inhibits the repassivation process.     

Corrosion behavior of CoCr films in Sulfuric acid

The corrosion behavior of CoCr films (∼500 to 1000 nm thick) deposited on glass by RF sputtering has been examined by classical electrochemical methods which provide a simple and rapid means for comparing one material with another. The development of a specially designed holder to allow electrical contact to the film and exposure to a sulfuric acid electrolyte was required. A comparison of potentiodynamic polarization curves for films containing various amounts of Cr with similar data from the literature for bulk CoCr alloys showed analogous behavior in the shape of the curve and in the level of Cr required to produce passivity, about 15-17%. Results indicate the formation of a passive layer containing a chromium oxide. In addition, comparison of an as-received sample with an electrochemically treated sample using Auger electron spectroscopy along with polarization results showed that Co oxides are apparently stabilized by the presence of Cr. Auger results also suggest that corrosion and passivation occur along the spaces or crevices between columnar grains during electrochemical treatment as indicated by the presence of a significant oxygen content.     

Effect of dissolved oxygen on electrochemical corrosion behavior of 2205 duplex stainless steel in hot concentrated seawater

The corrosion behavior of 2205 duplex stainless steel was investigated in hot concentrated seawater with different dissolved oxygen(DO) concentration by electrochemical measurement techniques and surface analysis methods. DO obviously enhances the cathodic reaction process, the formation of passive film and polarization resistance. With increasing the DO concentration from 0.34 to 3.06 mg L^-1, the relative contents of Fe₂O₃ and Cr₂O₃ and the Cr-enrichment gradually enlarge in the passive film. The higher DO concentrations result in lower defect densities and thicker of space charge layers in the passive films,whichmayeffectively inhibit the intrusion of aggressive chloride ions. The increment inDOconcentration clearly increases the pitting potential, but decreases the repassivation potential. It may weaken both the occurrence and repassviation tendencies of stable pitting corrosion.     

MHB4新型合金抗蚀性能研究

用中频感应炉熔炼了新型超低碳高合金奥氏体不锈钢ＭＨＢ４和３１６Ｌ不锈钢,研究了它们在不同介质中的抗腐蚀性能。结果表明,由于ＭＨＢ４增加了Ｃｒ、Ｎｉ、Ｍｏ的含量,并加入Ｗ,极大地提高了抵抗Ｃｌ＾－离子引起的点蚀能力,因此ＭＨＢ４的耐点蚀、耐缝隙腐蚀以及在合成海水中的抗蚀性均优于３１６Ｌ不锈钢。     

Extremely high pitting resistance of NiTi shape memory alloy thin film in simulated body fluids

In this paper the corrosion behavior of NiTi thin films fabricated by sputtering from Ni and Ti targets has been studied by cyclic potentiodynamic polarization tests in Hank's and Ringer's solution at 310 K. For comparison, bulk NiTi Shape Memory Alloy (SMA) has also been studied to elucidate the different corrosion behavior of bulk and thin film material. The electrochemical experiments reveal that thin film NiTi SMA has comparable corrosion current density (i_corr), much higher pitting corrosion potentials and wider passive range than the bulk NiTi. We show that NiTi SMA vapour deposited thin films are less susceptible to pitting corrosion than the bulk.     

Effects of sulfidation of passive film in the presence of SRB on the pitting corrosion behaviors of stainless steels

Pitting corrosion of stainless steels is a very complex process in the media with sulfate-reducing bacteria (SRB). Bacterial activities not only instantaneously affect the pit-initiation and the pit-growth, but also induce the changes of passive film in structure/properties and in turn affect the pitting corrosion behaviors of stainless steels as well. In this work, sulfidation of passive film in the cultures of SRB and its effects on the pitting corrosion behaviors of stainless steels were investigated by electrochemical techniques and X-ray photoelectron spectroscopy (XPS). As results showed, anodic cyclic polarization curves demonstrated that sulfidation caused a loss of passivity of stainless steels, but sulfidation happening in the short term is more detrimental than that in the long term; from standing point of cathodic depolarization of corrosion, sulfidation polarized the cathodic reactions to a greater extent, which means that sulfidation helps impede the pit-growth; XPS revealed that almost only iron oxides in the passive film were converted into sulfides in forms of FeS and FeS₂, while elements of Cr and Ni still remained essentially as oxides/hydroxides. So, in understanding the mechanisms of pitting corrosion of stainless steels in the media with SRB, effects of sulfidation of passive film must be taken into consideration.