再生水环境中304不锈钢生物膜腐蚀电化学特征

研究了以再生水作为循环冷却系统补水的北京某热电厂冷却塔底粘泥中分离纯化培养出来的硫酸盐还原菌(SRB)生长特性.采用原子力显微镜(AFM)、扫描电镜(SEM)、能谱分析仪(EDS)和电化学交流阻抗(EIS)方法研究了304不锈钢(SS304)表面生物膜特征及其主要成分和不锈钢/生物膜界面电化学行为.结果显示,再生水环境下304不锈钢表面形成的生物膜是由吸附的SRB菌体及以含碳有机物为主的胞外聚合物和FeS腐蚀产物构成.浸泡前期(前7 d)SS304电极表面阻抗值主要由SS304表面钝化膜的贡献;浸泡后期(14 d后),电极体系阻抗值由不锈钢表面钝化膜和生物膜共同贡献.     

Electrochemical Behavior of Stainless Steels for Sudomotor Dysfunction Applications

AISI 304L is used in Sudoscan^TM technology (Impeto Medical Inc.) for the early diagnosis of small fiber neuropathy caused by type‐2 diabetes or cystic fibrosis. In a recent paper, several substitute electrodes were analyzed, among which the biocompatible nickel‐free AISI 430 appeared as an interesting material. In the present work, we compare in details the electrochemical behavior of AISI 430 with respect to the reference AISI 304L, using Electrochemical Impedance Spectroscopy (EIS) in mimetic electrolytic solutions of sweat. Apart of being cheaper than AISI 304L, AISI 430 has roughly similar characteristics but is slightly more sensitive to chloride ions concentration and, according to EIS and SEM analyses, forms a thicker, more homogeneous and protective oxide layer, which makes it a convenient electrode material.     

EIS study on passive films of AISI 304 stainless steel in oxygenous sulfuric acid solution

Electrochemical impedance spectroscopy (EIS) and Kramers–Kronig (K–K) transforms were made on American Iron and Steel Institute (AISI) 304 stainless steel (SS) in naturally aerated sulfuric acid solution at room temperature. The K–K relations testify that the systems under investigation comply with the linearity, causality, and stability constraints of linear system theory (LST) and thereby validate the EIS data. The polarization resistance decreased with removing of passive film and pitting formed in the passive layer, due to layer thinning or pitting caused by chloride. The impedance data for 304 SS with passive films can be accurately modeled using individual components of the equivalent circuits. The polarization resistances (Rp) of the 304 SS can be confirmed by Nyquist plots and estimated from the anodic polarization curves. The reaction model of the dissolution‐passivation process of 304 SS in acid solution is proposed. Copyright © 2009 John Wiley & Sons, Ltd.     

镀锡薄钢板在功能饮料中的腐蚀行为

应用电化学阻抗谱(EIS)技术,结合扫描电镜(SEM)、能量散射X射线谱(EDS)、X射线光电子能谱(XPS)、扫描探针显微镜(SPM)等表面分析技术,研究了镀锡薄钢板在功能饮料中的腐蚀过程并探讨了腐蚀机制.结果表明:浸泡前期,EIS低频阻抗模值的增加与前31 h镀锡薄钢板表面形成的腐蚀产物膜有关;随着浸泡时间的增加,EIS低频阻抗模值有所下降,这与腐蚀产物膜的部分脱落以及暴露的基底金属碳钢的腐蚀有关.镀锡薄钢板在功能饮料中浸泡24天后其表面的腐蚀产物膜由外层的富锡层和内层的富铁层组成,XPS结果表明其成分主要是Sn(Ⅱ)/Sn(Ⅳ)与柠檬酸阴离子及Fe(Ⅲ)与柠檬酸阴离子组成的化合物,其腐蚀类型主要是功能饮料中的有机酸对镀锡薄钢板的腐蚀.     

Studying the fine microstructure of the passive film on nanocrystalline 304 stainless steel by EIS,XPS, and AFM

The fine microstructure of the passive films on nanocrystalline (NC) and coarse crystalline (CC) 304 stainless steels (SSs) in 0.5 M H₂SO₄ were investigated by electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The results indicate that the passive film on both CC and NC SSs exhibits a two-layer microstructure consisting of a compact inner layer and a porous outer layer. Some hydrated compounds (HC) were present in the porous outer layer of NC SS but not CC SS in 0.5 M H₂SO₄ solution. The pores in the outer layer of the NC SS were observed to be in the nanoscale by AFM. HC filling of the pores in the passive film on NC SS may occur due to capillary forces endowed by the nanosize pores. XPS analysis of the passive films on both CC and NC SSs, however, does not show such a composition difference which is attributed to dehydration occurring in the XPS vacuum chamber. Both the inner and outer layers of the NC SS were determined by EIS analysis to be more compact and protective than the corresponding films on CC SS as evidenced by the lower Q value, higher n, and much higher R value in the corresponding layer.     

Corrosion resistance of amorphous AlPO4 coating in salty atmospheres

The objective of the present study was to introduce a cost-effective and environmentally friendly coating to improve the corrosion resistance of the structures located in salt water. The coating solution, based on amorphous aluminum phosphate composition, was synthesized by sol–gel process and applied to AISI 304 stainless steel by dip coating technique. X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy analyses were employed to investigate the phase composition and morphology of the coating. Corrosion behavior of the uncoated and coated samples was investigated using standard salt spray test, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) in 3.5 wt.% NaCl solution. Salt spray test results for the bare substrate revealed a corrosion rate of six-time greater than that of the coated surface after 168 hr exposure time. Electrochemical test results declared that the amorphous AlPO₄ coating decreased the corrosion current density of the AISI 304 stainless steel by 10 orders of magnitude. Furthermore, according to the corresponding EIS measurements, the coated surface exhibited a superior anti-corrosion performance than uncoated sample. Overall, the results declared that the amorphous AlPO₄ coating could be a good choice for surface protection of stainless steel against electrochemical corrosion in salty environments.     

Electrochemical and XPS studies on corrosion behaviours of AISI 304 and AISI 316 stainless steels under plastic deformation in sulphuric acid solution

The corrosion behaviours of austenitic stainless steels were investigated by electrochemical methods under plastic deformation with constant strain in the naturally aerated 0.5 M H₂SO₄ + 0.2 M KCl solution at room temperature. The work addresses the influence of plastic deformation and molybdenum element on the corrosion resistance of austenitic stainless steels in the test solution. Electrochemical impedance spectroscopy presents the decreasing charge transfer resistance (R_t) and polarization resistance (R_p) values with the immersion time for AISI 304 stainless steel under constant strain deformation, and the increasing R_t and R_p values with the immersion time for AISI 316 stainless steel. The analysis of the chemical composition of the corrosion products was carried out by XPS. Molybdenum addition in AISI 316 stainless steel affects significantly the corrosion resistance because of its high ability to form Mo (VI) and MoCl₅ insoluble compounds in acid medium. Copyright © 2011 John Wiley & Sons, Ltd.     

Growth behaviour of cerium-based conversion coating on Zn-5%Al alloy

Cerium-based conversion coatings were deposited on a Zn-5%Al alloy by immersing the alloy in cerium nitrate aqueous solutions with various immersion times. The growth behaviour of the cerium-based conversion coating on the Zn-5%Al alloy was investigated by the electrochemical impedance spectroscopy (EIS), SEM, energy dispersive spectroscopy (EDS), and XPS techniques. The results reveal that the coating mainly consists of ZnO, Zn(OH)₂, Ce(OH)₄, Ce(OH)₃, CeO₂, and Ce₂O₃. The growth of the cerium-based conversion coating is accompanied by metal dissolution. The dissolution mainly occurs on the η-Zn surface of the phase boundary and continues to extend to the Zn-rich phase as the coating grows. EIS results show that with increasing immersion time, the corrosion resistance of the Ce conversion coating gradually increases in the early growth stage and then decreases when the cracks appear.     

Nanoindentation studies and modeling of surface layers on austenitic stainless steels by extreme electrochemical treatments

The nanoindentation studies were performed on two austenitic stainless steels, AISI 304L and 316L. The steel samples have undergone two different electrochemical treatments, standard (EP50) and a high‐current density electropolishing (EP1000). Firstly, the observations of the steels' surfaces were done with the optic images of the AISI 304L and 316L SS after these two treatments displayed. Presented in the paper results have shown clearly that the high‐current density close to 1000 A/dm² allows for obtaining the passive nanolayers with other mechanical properties than those obtained after a standard electropolishing (EP50). The prediction of these results has been confirmed by the preliminary XPS studies allowing for modeling of the steels' surface layers. The main finding of the study is revealing a new method of electrochemical treatment (EP1000) allowing to obtain the reduced Young's modulus of the stainless steels lower than that obtained after EP50. This feature is of high importance regarding the use of these steels as biomaterials. Copyright © 2015 John Wiley & Sons, Ltd.     

EIS and XPS studies on passive film of AISI 304 stainless steel in dilute sulfuric acid solution

Electrochemical impedance spectroscopy and XPS studies on AISI 304 stainless steel in naturally aerated 0.5 M H₂SO₄ solution were carried out at room temperature. The valuable model of the metal/solution interphase was established, and the reliable equivalent electrical circuits in the solution were presented. The analysis of the chemical composition of passive film on AISI 304 stainless steel was carried out by XPS. The passive film of AISI 304 stainless steel is composed of oxyhydroxides, Fe₂O_3, FeO, Cr₂O₃, NiO, sulfate, sulfite, and sulfide (FeS, NiS). It is reported that the ferrous sulfide film formed on AISI 304 stainless steel in the dilute sulfuric acid solution. The possible process in which sulfuric acid is reduced to sulfite and sulfide is proposed. The galvanic interaction of sulfide inclusions with the base alloy is introduced. Copyright © 2011 John Wiley & Sons, Ltd.     

Microbiologically-influenced corrosion of the electroless-deposited NiP-TiNi – Coating

In this study, we reveal the microbiologically influenced corrosion (MIC) behavior of the new electroless NiP-TiNi nanocomposite coating in simulated seawater using the electrochemical impedance spectroscopy (EIS) technique after different periods of incubation time (7, 10, 14, 21, 28 days) in a sulfate-reducing bacteria (SRB) medium. The biofilm formation and the corrosion products were characterized using the scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS). The EIS results revealed the carbon steel (CS)/NiP-TiNi and NiP-TiNi/SRB biofilm interfaces' characteristics after different incubation times in the SRB media. EIS measurements revealed that the NiP-TiNi nanocomposite coating's MIC resistances are superior relative to API X80 carbon steel and a TiNi-free NiP coating, with ∼93% of corrosion inhibition efficiency after 28 days of incubation.     

Preparation and characterization of palladium/polypyrrole-reduced graphene oxide/foamed nickel composite electrode and its electrochemical dechlorination of triclosan

In this study, a new composite electrode of palladium (Pd) nanoparticles dispersed on polypyrrole-reduced graphene oxide (PPy-rGO) loaded on foam-nickel was achieved by galvanostatic method. Characterization of structures, morphology and crystallinity of the synthesized materials were investigated by scanning electron microscopes (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy and electrochemical impedance spectroscopy (EIS). The results of XPS and XRD demonstrated Pd showed primarily as Pd0. From SEM and TEM results, we had seen that Pd nanoparticles were dispersible well on the composite electrode. Raman spectroscopy was used to show the state of graphene oxide and further demonstrated that PPy and rGO had existed of on the foam Ni matrix. The data of EIS also suggested the charge transfer of the new composite electrode decreased compared to Pd/PPy/foam-Ni and PPy/foam-Ni composite electrodes. The effect of the electropolymerization potential on Pd/PPy-rGO/foam-Ni electrode for removing triclosan (TCS) was examined. It was found that the removal efficiency of TCS on the composite electrode could reach 100% at electropolymerization potential of 0.7 V and reaction time of 100 min.     

硫脲对块体纳米晶工业纯铁在盐酸溶液中的缓蚀行为

采用电化学阻抗谱(EIS)研究了硫脲对室温下1 mol•L－1盐酸溶液中粗晶和纳米晶工业纯铁的腐蚀行为的影响.从EIS的拟合结果得知,在1 mol•L－1盐酸溶液中,块体纳米晶工业纯铁比粗晶工业纯铁腐蚀倾向小.基于纳米晶和粗晶工业纯铁在添加有硫脲的1 mol•L－1盐酸溶液中阻抗谱随浸泡时间的变化关系,观察到以下现象,当浸泡时间短至5 min时,对应不同浓度(50、100、150、500 mg•L－1)的缓蚀剂添加量,在粗晶工业纯铁的阻抗复平面图上出现一感抗弧,而在纳米晶工业纯铁的阻抗复平面图是一圆心下偏的容抗弧.随着浸泡时间的延长,两种样品的容抗弧半径增大,在150 mg•L－1的浓度时,电荷传递电阻(Rct)出现极值,这表明硫脲是一种吸附型缓蚀剂.抗盐酸腐蚀性能的提高和没有感抗弧的出现, 归因于体纳米化的结果,这与体纳米化的制备技术密切相关.     

Inhibition effect of hexadecyl pyridinium bromide on the corrosion behavior of some austenitic stainless steels in H2SO4 solutions

The inhibition effect of hexadecyl pyridinium bromide (HDPB) as a cationic surfactant on the corrosion behavior of some Egyptian austenitic stainless steel SS 304L, SS 316H and SS 304H in 0.5 M H₂SO₄ solutions was investigated by using potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS). The results indicate that HDPB is a good inhibitor for the samples under investigation in 0.5 M H₂SO₄ solutions. In addition, the inhibition efficiency η% increases with the inhibitor concentration while decreases with the increasing temperature referring to physical adsorption. The adsorption of the inhibitor obeys a Temkin adsorption isotherm. Polarization curves show that HDPB is a mixed inhibitor in H₂SO₄ solutions. The results obtained from polarization and impedance measurements are in good agreement. Activation-free energies, enthalpies, and entropies for the inhibition process of HDPB were determined.     

Surface Modification of 316L Stainless Steel by Grafting Methoxy Poly(ethylene glycol) to Improve the Biocompatibility

Percutaneous coronary intervention(PCI) has become an important method for the treatment of the patients with coronary heart disease; however, problems, such as vascular endothelial inflammation, late thrombosis, and stent restenosis still exist as a result of poor biocompatibility of the materials. To enhance the biocompatibility, methoxy poly(ethylene glycol)(mPEG) was immobilized on the surface of AISI 316 grade stainless steel(SS)(AISI: American Iron and Steel Institute). First, silanized mPEG was synthesized by the direct coupling of mPEG with 3-isocyanatopropyltriethoxysilane(IPTS) via urethane bonds, and the silanized mPEG was then grafted on the surface of SS that was hydroxylated with piranha solution. The results obtained from contact angle goniometry, X-ray photoelectron spectroscopy(XPS), and atomic force microscopy(AFM) confirm that the mPEG modified steel contained more C and Si and less Fe and Cr on its surface, exhibiting a morphological change and decrease in the contact angle. The biocompatibility of the mPEG modified SS was evaluated with fibrinogen adsorption, platelet activation and adhesion, and human umbilical vein endothelial cell(HUVEC) adhesion. Fibrinogen adsorption, platelet activation, and adhesion were clearly suppressed on the surface-modified steel. In addition, human umbilical vein endothelial cell(HUVEC) could adhere and proliferate on the surface of the mPEG-modified SS. This study indicates that the modification of 316L SS with mPEG could enhance the biocompatibility and provide a primary experimental foundation for the development of next-generation coronary stent materials for clinical application.     

溶胶-凝胶-水热晶化法制备锐钛矿TiO2纳米膜的耐蚀性能

以钛酸正丁酯为前驱体, 采用溶胶-凝胶-水热晶化法在不锈钢(SS)表面制备TiO₂纳米膜. 利用X射线衍射(XRD)、Raman光谱、场发射扫描电子显微镜(SEM)、原子力显微镜(AFM)和俄歇电子能谱(AES)表征了TiO₂纳米膜的晶型、表面形貌和表面化学组成. 通过极化曲线和电化学阻抗谱(EIS)研究了TiO₂纳米膜的耐蚀性能. 170 °C下水热晶化制备的锐钛矿TiO₂与450 °C焙烧制备的锐钛矿TiO₂的结晶度类似, 但两种TiO₂薄膜的表面结构存在明显差异, 水热晶化法制备的TiO₂纳米膜在3.5% (w) NaCl溶液中的耐蚀性能优于焙烧法制备的.     

AZ31和AZ61镁合金在模拟海水中的腐蚀电化学行为

应用极化曲线、电化学阻抗谱方法研究了两种Mg-Al-Zn系合金——AZ31和AZ61在模拟海水中的腐蚀电化学行为.根据两种镁合金在浸泡过程中腐蚀介质pH值的变化以及扫描电子显微镜对合金微观金相组织和腐蚀形貌的观察,讨论了镁合金的腐蚀机理及合金元素Al的含量对镁合金耐蚀性能的影响.结果表明,AZ61镁合金具有比AZ31镁合金更好的耐蚀性能,其原因主要是AZ61镁合金中Al含量较高使合金的微观组织结构更有利于耐蚀性能的提高.     

EIS studies of the destruction behavior of a corrosion inhibitor film on carbon steel surface under hydrodynamic conditions

Effect of surface water shear stress on the performance of an inhibitor film used in the carbon steel pipelines for oil and gas product transportation is studied. Experiments were conducted in laboratory by electrochemical impedance spectroscopy (EIS). EIS that was carried out under various rotation rates, different temperature, and immersion time was taken to investigate the behavior of a corrosion inhibitor and the destruction process. Typical EIS spectral changes were acquired during the film destruction processes, and this means that EIS is an effective method for evaluating inhibitor performance and monitoring the film layers’ behavior. Experimental results show that the film layers become more porous with increase in rotation rates and temperature. Therefore, the performance of this corrosion inhibitor decreased resulting from surface shear stress and bubble impact. In addition, scanning electron microscopy (SEM) was also taken to help confirm the inhibitor film structure under different conditions.     

硫酸溶液中1,1’-硫代羰基二咪唑在碳钢上的吸附及缓蚀影响和碘离子的增强效应

The inhibition effect of 1,1’-thiocarbonyldiimidazole (TCDI) on the corrosion behaviors of mild steel (MS) in 0.5 mol·L -1 H2SO4 solution was studied with the help of potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and linear polarization resistance (LPR) techniques. The effect of immersion time on the inhibition effect of TCDI was also investigated over 72 h. For the long-term tests, hydrogen evolution with immersion time (VH2-t) was measured in addition to the three techniques already mentioned. The thermodynamic parameters, such as adsorption equilibrium constant (Kads) and adsorption free energy (⊿Gads) values, were calculated and discussed. To clarify inhibition mechanism, the synergistic effect of iodide ion was also investigated. The potential of zero charge (PZC) of the MS was studied by electrochemical impedance spectroscopy method, and a mechanism of adsorption process was proposed. It was demonstrated that inhibition efficiency increased with the increase in TCDI concentration and synergistically increased in the presence of KI. The inhibition efficiency was discussed in terms of adsorption of inhibitor molecules on the metal surface and protective filmformation.     

Impact of sensitization on dissolution process of AISI 304 stainless steel during intergranular corrosion evaluated using DEIS technique

The paper presents the results of instantaneous impedance changes measurements vs. reactivation potential performed by means of dynamic electrochemical impedance spectroscopy (DEIS) technique for AISI 304 stainless steel (SS) dissolution process during intergranular corrosion (IG) in 0.5 M H₂SO₄ + 0.01 M KSCN solution. With the use of DEIS method, it was possible to estimate dynamic changes of the examined system’s impedance in conditions of proceeding IG process. Furthermore, the paper proposes an alternative way of evaluating AISI 304 stainless steel dissolution rate during intergranular corrosion based on approximation to theory of iron dissolution in sulfuric acid medium. Simultaneously, based on the DEIS measurements, information about the degree of sensitization of the examined material were obtained. Performed research revealed the advantages of the DEIS technique over the classical double-loop electrochemical potentiokinetic reactivation tests when investigating intergranular corrosion process.