20/316L双金属管的腐蚀失效原因分析

随着20/316L双金属管在油气生产中的推广应用,关于内衬316L不锈钢的腐蚀失效问题日益突出,尤其是条件苛刻的酸性集输环境下,目前相关研究不多.利用扫描电镜(SEM)、能谱仪(EDS)等测试手段对20/316L双金属管在含H2S-Cl-的酸性集输环境中出现的腐蚀失效问题进行了系统分析,探讨了腐蚀失效的原因.结果表明:20/316L双金属管腐蚀类型为局部腐蚀,主要分布于内衬管316L的底部.腐蚀失效的主要原因是腐蚀介质中存在高浓度的H2S与Cl-,共同促进了钝化膜的破裂与点蚀的发展.当存在较高浓度的H2S与Cl-时,钝化膜薄弱处与电位较低的非金属夹杂物处易发生钝化膜的破裂与金属基体的快速溶解而成为点蚀源,形成点蚀.     

Distinction of the two phases of CuTCNQ by scanning electrochemical microscopy

The two known phases of CuTCNQ and TCNQ (TCNQ = 7,7',8,8'-tetracyanoquinodimethane) have been probed by scanning electrochemical microscopy (SECM) in the feedback mode. The first use of this technique for distinguishing differences in the electronic properties of semiconductor phases exploits the large differences in conductivity that exist between CuTCNQ and the parent TCNQ material and also between the CuTCNQ phases I and II. However, the packing density of the individual CuTCNQ crystals in a film structure also is shown to influence the SECM feedback response. Finally, it is shown that films of pure phase II material or mixtures of the phases can be mapped using feedback mode SECM. The SECM method provides valuable insights for elucidating properties of semiconducting solids that are mounted on insulating substrates.     

Microelectrode array microscopy: investigation of dynamic behavior of localized corrosion at type 304 stainless steel surfaces

Scanning electrochemical microscopy (SECM) and a recently developed microelectrode array microscope have been used to study localized corrosion and electron-transfer characteristics of native oxide layers of type 304 stainless steels. The I-/I3- redox couple was employed as a mediator and allowed sensitive detection of oxide breakdown events. In solutions containing I-, a signal at the microelectrode was observed on type 304 stainless steel surfaces at active pitting corrosion sites. Under conditions where pitting corrosion occurs, SECM was used to track the temporal characteristics of the reaction in a spatial manner. However, because of the time required to create an image, much of the temporal information was not obtained. To improve the temporal resolution of the measurement, microelectrode array microscopy (MEAM) was developed as a parallel method of performing SECM. The demonstration shown reveals the potential of MEAM for analysis of surface chemistry on temporal and spatial domains.     

Electrochemical formation of highly pitting resistant passive films on a biomedical grade 316LVM stainless steel surface

The results discussed in the paper demonstrate that a significant improvement in pitting corrosion resistance of a biomedical grade 316LVM stainless steel can be achieved by electrochemically forming highly-protective passive oxide films on the material's surface, under cyclic potentiodynamic polarization conditions. The film formed in a sodium nitrate electrolyte is completely resistant to pitting corrosion in simulating physiological solutions even at high temperatures (60 °C), and after sterilization. The high pitting resistance of the electrochemically-formed films was explained on the basis of their semiconducting properties. Namely, the enrichment of the outer part of the electrochemically formed passive film with Cr(VI)-species results in a decrease in the density of oxygen vacancies, which act as pitting initiation sites, and their ‘replacement’ by metal vacancies formed by the electrochemical oxidation of Cr(III) to Cr(VI). In this configuration, the outer Cr(VI)-rich oxide layer behaves as cation selective, which results in the increased pitting corrosion resistance of the film. The simple electrochemical passivation technique discussed in the paper can be efficiently used to form highly pitting resistant passive films on 316LVM-built medical implant devices of any geometry.     

Application of scanning electrochemical microscope in the study of corrosion of metals

Scanning electrochemical microscope (SECM) has become a very useful and powerful technique for probing a variety of electrochemical reactions in corrosion process due to its high spatial resolution and electrochemical sensitivity to characterize the topography and redox activities of the metal/electrolyte solution interface. Its capability for the direct identification of chemical species in localized corrosion processes with high spatial resolution would be more advantageous compared to other local probe techniques with only morphological characterization. In this review, the applications of the SECM in the study of early stages of localized corrosion, electroactive defect sites in passive films, local initiation of pits, degradation of coating properties on steels, and some combined methods through SECM integrated with other techniques have been summarized and commented. Finally, the optimization for SECM’s experiment design and operation as well as foreseeable application range has been proposed.     

Assessment of the electrochemical behavior of two-dimensional networks of single-walled carbon nanotubes

Scanning electrochemical microscopy (SECM) has been employed in the feedback mode to assess the electrochemical behavior of two-dimensional networks of single-walled carbon nanotubes (SWNTs). It is shown that, even though the network comprises both metallic and semiconducting SWNTs, at high density (well above the percolation threshold for metallic SWNTs) and with approximately millimolar concentrations of redox species the network behaves as a thin metallic film, irrespective of the formal potential of the redox couple. This result is particularly striking since the fractional surface coverage of SWNTs is only approximately 1% and SECM delivers high mass transport rates to the network. Finite element simulations demonstrate that under these conditions diffusional overlap between neighboring SWNTs is significant so that planar diffusion prevails in the gap between the SECM tip and the underlying SWNT substrate. The SECM feedback response diminishes at higher concentrations of the redox species. However, wet gate measurements show that at the solution potentials of interest the conductivity is sufficiently high that lateral conductivity is not expected to be limiting. This suggests that reaction kinetics may be a limiting factor, especially since the low surface coverage of the SWNT network results in large fluxes to the SWNTs, which are characterized by a low density of electronic states. For electroanalytical purposes, significantly, two-dimensional SWNT networks can be considered as metallic films for typical millimolar concentrations employed in amperometry and voltammetry. Moreover, SWNT networks can be inexpensively and easily formed over large scales, opening up the possibility of further electroanalytical applications.     

氯离子对球墨铸铁管土壤腐蚀影响机理研究

基于埋片加速腐蚀试验,采用电化学阻抗谱测量和微观分析技术,研究了氯离子(Cl~-)对球墨铸铁腐蚀规律、腐蚀层结构以及腐蚀产物的影响。主要结论如下:(1)球墨铸铁主要发生局部腐蚀,且随Cl~-含量的增加,腐蚀速率增大,出现严重腐蚀坑;其腐蚀坑深与腐蚀时间成幂函数关系,当Cl~-含量高于0.515%时,局部腐蚀情况尤为严重。(2)球墨铸铁腐蚀经历点蚀诱导期、点蚀发展期和稳定腐蚀期3个阶段;在前两个阶段电荷传递为腐蚀速率控制步骤,第三个阶段转变为氧的扩散控制。(3)腐蚀产物主要为铁的氧化物和羟基氧化物;高Cl~-环境下产生的β-Fe OOH和铁的羟基氯化物均能加速球墨铸铁的电化学腐蚀。     

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.     

Effects of 5-(3-aminophenyl)-tetrazole on the inhibition of unalloyed iron corrosion in aerated 3.5% sodium chloride solutions as a corrosion inhibitor

The effects of 5-(3-aminophenyl)-tetrazole (APT) on the inhibition of unalloyed iron corrosion in aerated 3.5% NaCl solutions as a corrosion inhibitor have been studied using open circuit potential (OCP), cyclic potentiodynamic polarization (CPP), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) measurements. The inhibited iron surface was characterized by scanning electron spectroscopy (SEM) and energy dispersive X-ray (EDS) investigations. The OCP showed positive shifts of potential in the presence of APT and the increase of its concentration. CPP and CA measurements indicated that APT molecules decrease the pitting and uniform corrosions through decreasing the pitting and absolute currents, and corrosion rate as well as shifting the corrosion and pitting potentials of iron towards the noble values. EIS plots revealed that APT increases the surface and polarization resistances of iron. SEM/EDS investigations proved that the inhibition of iron corrosion in NaCl containing APT solutions is achieved by the adsorption of APT molecules onto iron to preclude the dissolution process by blocking the active sites on its surface.     

Local feedback mode of scanning electrochemical microscopy for electrochemical characterization of one-dimensional nanostructure: theory and experiment with nanoband electrode as model substrate

Local feedback mode is introduced as a novel operation mode of scanning electrochemical microscopy (SECM) for electrochemical characterization of a single one-dimensional (1D) nanostructure, for example, a wire, rod, band, and tube with 1-100-nm width and micrometer to centimeter length. To demonstrate the principle, SECM feedback effects under diffusion limitation were studied theoretically and experimentally with a disk probe brought near a semi-infinitely long band electrode as a geometrical model for a conductive 1D nanostructure. As the band becomes narrower than the disk diameter, the feedback mechanism for tip current enhancement is predicted to change from standard positive feedback mode, to positive local feedback mode, and then to negative local feedback mode. The negative local feedback effect is the only feedback effect that allows observation of a 1D nanostructure without serious limitations due to small lateral dimension, available tip size, or finite electron-transfer rate. In line-scan and approach-curve experiments, an unbiased Pt band electrode with 100-nm width and 2.6-cm length was detectable in negative local feedback mode, even using a 25-microm-diameter disk Pt electrode. Using a 2-microm-diameter probe, both well-defined and defected sites were observed in SECM imaging on the basis of local electrochemical activity of the nanoband electrode. Noncontact and spatially resolved measurement is an advantage of this novel SECM approach over standard electrochemical approaches using electrodes based on 1D nanostructure.     

Effects of alloying elements on the electrochemical characteristics of iron aluminides

Effects of alloying elements on the electrochemical characteristics of iron aluminides in the H2SO4, H2SO4+KSCN and HCl solutions were investigated using electrochemical tests. The corrosion morphologies in iron aluminides were analysed by utilising optical microscopy. It was found that the addition of Cr and Mo to iron aluminides increased the corrosion potential, pitting potential and repassivation potential. The active current density, passive current density and reactivation current density decreased as Cr and Mo were added. In the case of Mo addition, the passive current density was slightly higher in the H2SO4 solution than in solutions containing SCN- and Cl-. When B was added to samples, the corrosion potential and repassivation potential decreased, whereas the active current density, passive current density, reactivation current density and pitting potential increased. Iron aluminides containing Mo and Cr showed remarkably improved intergranular and pitting corrosion resistance to SCN- and Cl- solution. On the other hand, B addition accelerated granular and intergranular corrosion by precipitation of borides. This revised version was published online in November 2006 with corrections to the Cover Date.     

Mechanisms of hardening, wear and corrosion improvement of 316 L stainless steel by low energy high current pulsed electron beam surface treatment

The mechanisms of corrosion and wear improvements by low energy high current pulsed electron beam (LEHCPEB) have been investigated for an AISI 316 L steel. Selective purification followed by epitaxial growth occurred in the top surface melted layer (2-3 μm thick) that was softened by tensile stresses and, to a much lower extent, by lower efficiency of MnS precipitation hardening. Electrochemical impedance spectroscopy and potentiodynamic polarization analyses used to model the corrosion behavior revealed that, while craters initiated at MnS inclusions initially served as pitting sites, the resistance was increased by 3 orders of magnitude after sufficient number of pulses by the formation of a homogeneous covering layer. The wear resistance was effectively improved by sub-surface (over 100 μm) work hardening associated with the combine effect of the quasi-static thermal stress and the thermal stress waves. The overall results demonstrate the potential of the LEHCPEB technique for improving concomitantly the corrosion and wear performances of metallic materials.     

EIS Study on Pitting Corrosion of AA5083-H321 Aluminum-Magnesium Alloy in Stagnant 3.5% NaCl Solution

In this research, EIS （electrochemical impedance spectroscopy） technique was utilized to study the pitting corrosion behaviour of AA5083-H321 aluminum-magnesium alloy in 3.5% NaCl solution. Impedance spectra were obtained during 240 h of exposure of the sample to the test solution. The surface and cross-section of the samples were studied by scanning electron microscopy （SEM） and EDAX （energy dispersive analysis of X-ray） analysis. The results indicated that as the resistance of the passive layer on intermetallic particles is very small, this parameter on the sample surface layers is controlled by that of pure passive layer. However, the capacitors in the proposed equivalent circuit are replaced with the constant phase elements （CPE）, due to non-uniformity and occurrence of pitting corrosion on the surface. The outward diffusion of Al^＋3 ions through the passive layer and the thickening of this layer cause the impedance decrease in the first 24 h and increase afterwards. The detachment of intermetallic particles from some of pits and the accumulation of the corrosion products inside some others are factors that prevents the continuation of cathodic reactions on the top of the intermetallic particles.     

钙处理对AH36船体钢耐点蚀性能的影响

为提高AH36钢的耐海水腐蚀性能,炼钢时引入了钢水钙处理工艺.本文通过室内间浸挂片试验、交流阻抗试验、动电位极化试验及极化试验后的SEM分析,研究了钙处理对AH36钢中的夹杂物及耐点蚀性能的影响.结果表明:变性夹杂物中的CaS对钙处理钢的耐点蚀性能有明显的影响.通过钙处理把钢中氧化铝夹杂、硅铝酸盐夹杂等球化变性成无CaS或低CaS的球状CaO-Al2O3复合夹杂,可有效提高钢的耐点蚀性能;变性球状复合夹杂中含较多的CaS会促进诱发夹杂物周围基体腐蚀,提高点蚀诱发敏感性;含硫量较高的AH36钢在钙处理不充分时,形成CaS夹杂或以CaS为主的复合夹杂,会使AH36钢的耐点蚀性能恶化.     

Electrochemical imaging of localized sandwich DNA hybridization using scanning electrochemical microscopy

Imaging of localized hybridization of nucleic acids immobilized on gold-DNA chip was performed by means of the feedback mode of scanning electrochemical microscopy (SECM). Thiol-tethered oligodeoxynucleotide (HS-ODN) probes, spotted on a gold surface, were hybridized with unmodified target sequence via sandwich hybridization with a biotinylated signaling probe. Spots where sequence-specific hybridization had occurred were developed by adding a streptavidin-alkaline phosphatase conjugate and biocatalyzed precipitation of an insoluble and insulating product. As a consequence, the surface conductivity of the spotted region of the chip where hybridization had taken place changed. These changes in conductivity were sensitively detected by the SECM tip. The proposed method allows imaging of a DNA array in a straightforward way. Analysis of real samples was also performed coupling this method with polymerase chain reaction. The imaging of 60 nM PCR amplicon (255 bp) was demonstrated.     

Pitting corrosion behavior of lead in Na2HPO4–NaNO3 solutions

The pitting corrosion behavior of lead in 0.10 M Na₂HPO₄ solutions containing various concentrations from NaNO₃ has been studied using potentiodynamic anodic polarization and SEM techniques and complemented by both X-ray and FT-IR surface analysis. Above certain critical NaNO₃ concentration, the aggressive anions prevented the oxygen evolution and induce pitting on the Pb electrode surface. Pitting-initiation and pitting-growth were found to depend on the concentration of the aggressive NO^– ₃ anions. Also, some changes in the (I–E) curves within the active, pre-passive and passive regions were recorded. These changes imply mainly the appearance of new stages and peaks. This behavior gives an indication for definite changes in the pit-characteristics, which interpreted in terms of solution composition and kinetics of its associated processes within pits.     

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.     

稀土处理对Mn-V-Ti钢点蚀性能影响的研究

实验室冶炼了5炉稀土处理及未处理的锰系低合金船体钢,并收集了一种工业生产的同种钢。通过冶金分析、极化试验、闭塞电池试验及挂片试验,研究了夹杂物变性对钢材点蚀诱发及扩展的影响;结果表明:钢中夹杂物是点蚀的诱发源,硫化物夹杂物的数量对钢材的点蚀性能有显著影响。稀土硫化物夹杂数量少,体积小,能显著降低钢的点蚀诱发敏感性,降低钢的蚀坑扩展速度,提高钢的耐蚀性。     

Surface modifications induced in 316L steel by laser peening and shot-peening. Influence on pitting corrosion resistance

The influence of laser peening (LP) on the electrochemical behavior of AISI type 316L stainless steel in a saline environment was evaluated. Surface modifications were investigated as they might have beneficial effects on the corrosion behaviour. Low residual stress and work hardening levels were found, when compared with a conventional shot-peening (SP) treatment, mainly because of the absence of martensite transformation in the case of LP. Surface changes were accompanied by small roughening effects and a global preservation of the surface chemistry after treatment. Therefore, electrochemical tests performed on samples after LP and SP treatments showed increases in rest potentials, reductions of passive current densities and anodic shifts of the pitting potentials evidenced by a stochastic approach of pitting. The better pitting resistance was observed after LP treatment, which seems to reflect a reduction or an elimination of active sites for pitting at lower potentials. Even though the deleterious surface state of shot peened surfaces possibly counterbalances the beneficial influence of residual stresses, a beneficial influence of mechanical surface treatments has been demonstrated regarding the localized corrosion properties.     

Pitting corrosion of steel tubes in an air preheater

Severe pitting corrosion of a carbon steel tube was observed in the air preheater of a power plant, which runs on rice straw firing. Approximately 1450 tubes were removed from Stage 3 of the preheater (air inlet and flue gas outlet) due to corrosion and local bursting. Samples from Stage 2 (where corrosion was low) and Stage 3 (severe corrosion) were taken and subjected to visual inspection, scanning electron microscopy (SEM), X-ray diffraction (XRD), microhardness measurement, and chemical and microstructural analysis. It was determined that extended non-operation of the plant resulted in the settlement of corrosive species on the tubes in Stage 3. The complete failure of the tube occurred due to diffusion of these elements into the base metal and precipitation of potassium and chlorine compounds along the grain boundaries, with subsequent dislodging of grains. The nonmetallic inclusions acted as nucleating sites for local pitting bursting. Nonuniform heat transfer in Stage 3 operation accelerated the selective corrosion of front-end tubes. The relatively high heat transfer in this stage resulted in condensation of some corrosive gases and consequent corrosion. Continuous operation of the plant with some precautions during assembly of the tubes reduced the corrosion problem.