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.     

A zirconia-polyester glycol coating on differently pretreated AISI 316L stainless steel: corrosion behavior in chloride solution

The effect of zirconia and zirconia-polyester glycol hybrid coatings on the corrosion resistance of mechanically polished or anodized AISI 316 stainless steel (316L), was studied by potentiodynamic polarization and electrochemical impedance spectroscopy in 0.1 M NaCl and scanning electron microscope and atomic force microscopy examinations. The deposition of zirconia coatings was achieved by the sol–gel technique by immersing the samples in either the inorganic polymer or the organic–inorganic polymer mixture. From potentiodynamic and impedance measurements, the grade of protection is reduced with the exposure time to the electrolyte, which is mainly associated with lost of film adhesion and, consequently, detachment from the metal substrate. However, the uncoated anodized sample revealed an unexpected corrosion behavior; the anodic film formed during anodizing readily increased the corrosion resistance of the 316L stainless steel in 0.1 M NaCl, revealing a considerable reduction in the corrosion current density and an increase in the pitting potential.     

Structural and electrochemical characterization of sputter-deposited nitrided NiCr alloys

Nickel-based coatings are potential candidates for the protection of electrochemical dissolution of steel surfaces. Such coatings, elaborated by magnetron sputtering in a nitrogen atmosphere, offer good corrosion protection, good adherence as well as stability for metallic structures. NiCr alloys with almost constant composition have been deposited with different nitrogen contents on stainless steel and carbon steel surfaces. The coating uniformity, homogeneity, composition and crystallinity have been studied by scanning electron microscopy, energy-dispersive X-ray spectrometry, atomic force microscopy and X-ray diffraction techniques. The corrosion degradation behavior of all the samples was tested in NaCl and NaCl and CO₂ mixture exposures using electrochemical impedance spectroscopy measurements. Nitrided NiCr alloys on a stainless steel substrate resulted with better adhesion than carbon steel, by delaying the corrosion mechanism when exposed to NaCl and CO₂ solution. A comparison of the corrosion resistive behavior of the substrates (stainless steel, carbon steel) and the coatings is made by using the electrical capacitance concept from a double-layer model for the coating–metal interface.     

Bioactive and Protective Sol-Gel Coatings on Metals for Orthopaedic Prostheses

The aim of this work has been the preparation and evaluation of sol-gel coatings for clinical applications. Research was focussed in the development of highly corrosion resistant and/or bioactive sol-gel coatings onto AISI 316L stainless steel. Hybrid SiO₂ sol-gel coatings inhibited corrosion and Fe diffusion, although no signal of bioactivity was detected. The inclusion of Ca- and P-alcoxides in the sol composition did not promote bioactivity. Bioactive coatings were obtained from suspensions prepared by adding glass (CaO·SiO₂·P₂O₅) particles to an hybrid organic-inorganic SiO₂ sol. The dissolution of glass particles promoted in vitro induction of apatite along with a slight reduction in the corrosion resistance of coated pieces. By combining an inner SiO₂ hybrid film acting as barrier against corrosion with an outer coating containing bioactive glass particles, a significant improvement in the electrochemical behaviour was observed. This double-layered coating showed in vitro signals of bioactivity, and preliminary in vivo tests gave promising results.     

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.     

The electrochemical synthesis of poly(o-phenylenediamine) on stainless steel and its corrosion protection ability in 3.5 % NaCl solution

In this study, electrochemical synthesis of poly(o-phenylenediamine) (PoPDA) on 316L stainless steel and its corrosion inhibition effect were studied. Electropolymerization of o-phenylenediamine (oPDA) was carried out by a potentiodynamic method using 0.5 M H₂SO₄ solution containing 0.05 M oPDA monomer. The corrosion protection ability of the PoPDA in 3.5 % NaCl was investigated by potentiodynamic polarization, electrochemical impedance spectroscopy, and change of open circuit potential with immersion time (E_OCP ? t). The results showed that PoPDA acted as a protective layer on stainless steel against corrosion in 3.5 % NaCl solution.     

溶胶-凝胶法制备改性TiO2纳米薄膜及其防腐蚀性能

应用溶胶-凝胶法和浸渍提拉技术在316L不锈钢表面分别制备TiO2纳米膜和 B-Fe-Ce改性的TiO2纳米膜. 采用场发射扫描电子显微镜(FE-SEM)、原子力显微镜(AFM)、拉曼光谱法和能量分散谱(EDS)对薄膜进行表征,通过电化学阻抗谱(EIS)和动电位阳极极化曲线的测试考察薄膜的耐蚀性及对不锈钢的保护性能. 结果表明:两种纳米薄膜均含锐钛矿型的TiO2纳米颗粒,纯TiO2纳米膜与改性后的纳米膜中颗粒直径分别约为15和10 nm. TiO2/316L不锈钢和 B-Fe-Ce-TiO2/316L不锈钢膜电极浸泡在0.5 mo.lL-1 NaCl溶液后,后者的电化学反应电阻较大,动电位阳极极化曲线的稳定钝化区较宽,击穿电位更高,说明改性的纳米膜的耐蚀性及其保护性能更好.     

Effect of sulfate and dissolved hydrogen on oxide films on stainless steel in high-temperature water

In the present paper, we focus on the influence of sulfate ion impurity and dissolved hydrogen on the protective ability of the oxide film on stainless steel in high-temperature water. For the purpose, the electrical and electrochemical properties of oxide films formed on AISI 316L NG in simulated boiling water reactor crack conditions (10 ppm sulfate purged with N₂ + 0.01 or 0.5% H₂) were characterized by in situ electrochemical impedance spectroscopy (EIS). In addition, the surface and in-depth composition of the oxide films has been estimated by ex situ Auger electron spectroscopy (AES). The quantitative assessment of the protective ability of the oxide is based on an interpretation of the electrochemical impedance data per the mixed-conduction model. A novel procedure for the estimation of kinetic and transport parameters that involves comparison of the model equations to both EIS and AES results is proposed and tested. Based on the parameter values, the effect of sulfate and dissolved hydrogen on the processes of film growth and dissolution is discussed in view of an approach to the initiation of stress corrosion cracks.     

Effect of Sintering Temperature on the Corrosion and Wear Behavior of Protective SiO2-Based Sol-Gel Coatings

Sol-gel hybrid organic-inorganic and inorganic SiO₂-based protective coatings with and without added 3 m glass particles were developed and tested for their corrosion and wear behavior of an stainless steel substrate (AISI316L). The corrosion resistance greatly increases by incorporating glass particles in the sols. The incorporation of particles in the coatings allows the synthesis of thicker crack-free coatings. On the other hand, the corrosion resistance increases for coatings with a higher organic content obtained at lower sintering temperature. These coatings are also highly stable in saline aqueous solutions. However, the wear resistance is badly affected by the hybrid character of the SiO₂ matrix. The optimum coating process in terms of corrosion and wear resistance, appears to be a hybrid system with a dense SiO₂ network achieved at intermediate sintering temperatures.     

Evaluation of passive film behaviour of super austenitic stainless steels at different potential regions using dynamic electrochemical impedance spectroscopy

Potentiodynamic anodic polarisation and dynamic electrochemical impedance spectroscopic (DEIS) measurements were carried out on 316L stainless steel and alloys 926 and 31 in natural seawater in order to assess the crevice corrosion resistance. DEIS measurements were performed over a wide range of potentials covering the corrosion potential, passive region, breakdown region and dissolution region. The impedance measurements in potentiodynamic conditions clearly reveal the changes that occur in the passive layer with change in potential. The impedance spectra at different potential regions were also discussed elaborately. The surface morphology of the alloy after crevice corrosion was studied using optical microscope and atomic force microscopy.     

Study of the electrochemical behaviour of a carbon steel electrode in sodium sulfate aqueous solutions using electrochemical impedance spectroscopy

The study of a plain carbon steel (AISI 1020) in Na₂SO₄ aqueous solutions at different concentrations was carried out by electrochemical impedance spectroscopy (EIS) in order to determine the corrosion mechanism and to obtain representative corrosion rates of the system. EIS was used to measure corrosion current densities at high concentrations in the range 0.1–1 wt% Na₂SO₄, but in the low concentration range, from 0.001 to 0.01 wt%, a scattered Nyquist plot was obtained. Other electrochemical techniques, such as polarization resistance (PR), Tafel plots and electrochemical noise (EN), were also used in this analysis. The charge transfer resistance was determined and compared with the PR and noise resistance. Electronic Publication     

磁场对316L不锈钢微生物腐蚀行为的影响

采用循环极化、微生物分析法、扫描电镜及表面能谱分析等方法,研究了磁场对316L不锈钢在含硫酸盐还原菌(SRB)的土壤模拟溶液中的腐蚀行为。结果表明,磁场可以抑制SRB的生长;未外加磁场时316L不锈钢表面膜层以局部堆积为主,加有磁场时,局部堆积明显减小,膜层均匀致密的排列于基体表面;无论有或没有外加磁场,316L不锈钢表面均发生钝化膜破裂型点蚀,未外加磁场时的点蚀电位低于加有磁场时的。在相同的浸泡时间,未外加磁场时循环极化滞后环面积明显比加有磁场时的大,说明磁场可以有效抑制316L不锈钢点蚀的形成与发展,降低316L不锈钢的点蚀诱发能力。     

Corrosion sous contrainte de mono et polycristaux d'aciers inoxydables austenitiques en milieu MgCl2: Recherche d'ameliorations du comportement

The fractographic results of stress corrosion cracking of a 316L type austenitic stainless steel in MgCl₂ are in good agreement with the corrosion enhanced plasticity model. Based on the ideas of this model, the research of an improvement of the SCC resistance is attempted. It is shown that a cyclic prehardening can delay the initiation of the first microcracks and decrease the crack propagation velocity.     

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.     

Sol-gel ZrO2 coatings for chemical protection of stainless steel

ZrO₂ coatings deposited on 316 L stainless steel sheets were synthesized by sol-gel method using Zr(OC₃H₇)₄ as precursor and isopropanol, glacial acetic acid, and water as solvents for application with ultrasounds. Different solutions for dip-coating were prepared with compositions varying between 0.025 and 0.9 mol/dm³ of ZrO₂. X-ray diffraction shows that the films densified at 800°C are crystalline with a tetragonal structure. The thickness of the coatings varied from 0.35–0.75 m. The influence of the ZrO₂ coatings on the corrosion behavior of stainless steel substrates in aqueous NaCl was studied through potentiodynamic polarization curves at 1 mV/s. The values of the electrochemical parameters allow for an explanation of the role of the films in the increased resistance of steel against corrosion in moderately aggressive environments.     

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.     

TiO_2/316L不锈钢薄膜电极在NaCl溶液中的耐腐蚀性能

应用sol gel法和提拉技术于 316L不锈钢表面构筑纳米TiO2薄膜,再经水热后处理以消除膜中的细小龟裂.SEM和XRD技术表征膜的形貌和厚度,线性极化法分别考察膜厚度、pH、和Cl浓度对纳米膜电极耐腐蚀性能影响.电化学交流阻抗检测纳米TiO2膜在 0. 5mol/LNaCl溶液中的阻抗随浸泡时间的变化,光电子能谱技术测定了经浸泡 1008h后的纳米膜中各元素相对百分含量和价态.结果表明:在中性或碱性条件下,厚度为 375~464nm的纳米膜其耐腐蚀性随浸泡时间的延长呈现初期增加而后稳定,浸泡 48h后腐蚀电流较之浸泡初期降低 2个数量级,耐腐蚀电阻增加 2个数量级,在浸泡 1 008h内没有发现腐蚀的产物,Fe是以原子态扩散到膜中.     

Structure,hydrophilicity and corrosion resistance of sol–gel derived Ag-containing TiO2 film on plasma nitrided 316L stainless steel

Pure and Ag-containing TiO₂ films (Ag/Ti = 3.3 at.%) are coated on plasma nitrided 316L stainless steel by sol–gel method for biomedical applications. The addition of Ag does not cause obvious change in TG–DSC curves of the dried gels. The rough surface generated by plasma nitriding and the addition of Ag improve structural integrity of the TiO₂ films. X-ray diffraction reveals N loss and oxidation of the nitride layer during calcination treatment, and peaks of Ag or its oxides are not detected. X-ray photoelectron spectroscopy analysis indicates that Ag presents as metallic state in the film. Water contact angles of the coating samples decrease with UV irradiation treatment. The potentiodynamic polarization tests in a Ca-free Hank’s balanced salt solution show that the TiO₂ coated samples have decreased corrosion resistance due to N loss and oxidation of the nitride layer. The methods for crystallization of TiO₂ gel layers with minimized or avoided structural changes of the nitride layer will be tried in order to improve corrosion resistance of the duplex treated 316L stainless steel.     

Synthesis and evaluation of novel O-functionalized aminated chitosan derivatives as antibacterial,antioxidant and anticorrosion for 316L stainless steel in simulated body fluid

Chitosan’s Schiff base derivatives are taking the attention of scientists as a promising biomaterial for various applications. In this study, O-functionalized aminated chitosan (O-F-Am-Ch) was coupled with 4,4-dimethyl amino-benzaldehyde and N-methyl-2-pyrrolidone to produce Schiff bases (I) and (II), respectively. The chemical and physical properties of the new derivatives were investigated by Fourier transform infrared (FT-IR) that show a significant band for C=C between 1400 and 1600 cm⁻¹, thermal gravimetric analysis (TGA), which demonstrate an increase in the thermal stability of new derivatives than O-F-Am-Ch and scanning electron microscope (SEM) that indicates a slight increase in the rough structure of the surface. In addition, 2,2′-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and 2,2-Diphenyl-1-picrylhydrazyl (DPPH) assays that examined the antioxidant properties of the new Schiff bases. The biocidal activity against four different bacterial strains [two gram-negative (Pseudomonas aeruginosa and Escherichia coli) and two gram-positive (Bacillus cereus and Staphylococcus aureus)] demonstrates significant improvement of the inhibition activity compare to O-F-Am-Ch with more activity against Gram-negative bacteria than that against gram-positive bacteria.As an implanted alloy, 316L stainless steel is used as a temporary biomaterial in different countries without any pretreatment. Our study focused on further improving the alloy features by investigating the protection efficiency of O-F-Am-Ch and the synthesized Schiff bases for the 316L stainless steel surface against corrosion in simulated body fluid (SBF). The corrosion inhibition of these compounds was investigated using two electrochemical methods (potentiodynamic polarization technique and electrochemical impedance spectroscopy). The results suggested the formation of self-assembled monolayers (SAMs) of the compounds under investigation. Furthermore, they demonstrated a considerable dose-dependent inhibiting corrosion of 316L stainless steel in SBF, whereas the inhibition efficiency exceeds 77% at 1000 ppm for the Schiff bases II. In conclusion, the tested derivatives show promising properties to refine stainless steel for implant applications.     

Sol-gel coatings for chemical protection of stainless steel

Sol-gel thin coatings of ZrO₂, SiO₂, 70SiO₂-30TiO₂ and 88SiO₂-12Al₂O₃ compositions (mole %) have been prepared from sonocatalyzed sols and deposited by dip-coating technique on 316L stainless steel foils. The influence of the coatings on the chemical corrosion of the substrate has been measured through potentiodynamic polarization curves in aqueous 15% H₂SO₄ solution between 25 and 50°C. The values of the corrosion potential, polarization resistance and corrosion rate have been determined. Analysis of the data combined with scanning electron microscopy studies indicate that the films act as a geometric blocking against exposure to the corrosive media and increase the lifetime of the substrate up to a factor 8.5.