Electrochemical,SEM and XPS investigations on phosphoric acid treated surgical grade type 316L SS for biomedical applications

A simple surface pre-treatment method was attempted to establish a stable passive layer on the surface of surgical grade stainless steel (SS) of type 316L for biomedical applications. Surgical grade type 316L SS specimens were subjected to H₃PO₄ treatment for 1 h by completely immersing them in the acid solutions to develop a passive barrier film. The effect of various concentrations of phosphoric acid on the localized corrosion resistance behavior of type 316L SS was investigated through electrochemical techniques using cyclic polarization studies and electrochemical impedance spectroscopy (EIS). X-ray photoelectron spectroscopy (XPS) was used to evaluate the nature and composition of the passive films. The surface morphology and relative elemental composition of the untreated and acid treated surfaces subjected to anodic polarization was studied by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) techniques, respectively. Compared with untreated (pristine) 316L SS, the 40% acid treated surface formed a stable passive layer that had superior corrosion resistance.     

Study on the corrosion behavior of reinforcing steel in simulated concrete pore solutions using in situ Raman spectroscopy assisted by electrochemical techniques

In situ Raman spectroscopy, electrochemical impedance spectroscopy (EIS) and polarization curves were used to study the corrosion behavior of reinforcing steel in simulated concrete pore (SCP) solutions (saturated Ca(OH)₂ solutions). Results indicated that the reinforcing steel remained passive in chloride-free SCP solutions. However, the anodic polarization curve of the steel did not exhibit a stable passive region in the SCP solution with 0.5 M NaCl, the corrosion current density exceeded 0.1 μA cm⁻², the steel surface was unstable with chloride attack and localized corrosion appeared on it with FeCO₃ and Fe₂O₃ as the main corrosion products.     

Effect of stress on the passivation of Si-DLC coating as stent materials in simulated body environment

DLC coating can be used for vascular stents to prevent the stainless steel substrate from eluting Ni and Cr by plastic deformation and corrosion environment. The stress corrosion cracking (SCC) of Si-diamond-like carbon (Si-DLC) coated on 316L stainless steel was studied in a simulated body environment of a deaerated 0.89 wt.% NaCl electrolyte at 37 °C. This paper investigated the effect of Si-DLC coating on the SCC of 316L SS by slow-strain-rate test (SSRT), constant load test (CLT), and electrochemical impedance spectroscopy (EIS). The EIS data were monitored for the elastic and plastic regions under CLT to determine the electrochemical behavior of the passive film during SCC phenomena. The Si-DLC coated steel exhibited more ductility than uncoated steel and less susceptibility to SCC in this environment. According to X-ray photoelectron spectroscopy (XPS) analysis, the film repassivation occurs due to the presence of the silicon oxide layer on the Si-DLC film surface.     

Effect of ethylenediamine tetraacetic acid disodium on the corrosion of cold rolled steel in the presence of benzotriazole in hydrochloric acid

The inhibition behavior of cold rolled steel in 0.1 M hydrochloric acid (HCl) by ethylenediamine tetraacetic acid disodium (EDTA) in the absence and presence of benzotriazole (BTA) was investigated with Tafel polarization curve and electrochemical impedance spectroscopy (EIS). The polarization curve results show that the single EDTA acts as an anodic type inhibitor while the combination of EDTA and BTA acts as mixed type inhibitor and mainly inhibits anodic reaction. All impedance spectra in EIS tests exhibit one capacitive loop which indicates that the corrosion reaction is controlled by charge transfer process. Inhibition efficiencies obtained from Tafel polarization, charge transfer resistance (R_t) are consistent. The corrosion of cold rolled steel in 0.1 M HCl is obviously reduced by EDTA in combination with lower concentrations of BTA. Fourier transform infrared spectroscopy (FTIR) and atomic force microscopy (AFM) were used to characterize the corrosion surface of cold rolled steel. Probable mechanisms are present to explain the experimental results.     

THE EFFECT OF ENVIRONMENTALLY BENIGN FRUIT EXTRACT OF SHAHJAN (MORINGA OLEIFERA) ON THE CORROSION OF MILD STEEL IN HYDROCHLORIC ACID SOLUTION

The inhibition of the corrosion of mild steel in hydrochloric acid solution by the fruit extract of shahjan (Moringa oleifera) was studied using weight loss, electrochemical impedance spectroscopy (EIS), linear polarization, and potentiodynamic polarization techniques (Tafel). Inhibition was found to increase with increasing concentration of the extract. The effect of temperature, immersion time, and acid concentration on the corrosion behavior of mild steel in hydrochloric acid solutions with addition of extract was also studied. The inhibition occurred via adsorption of the inhibitor molecules on the mild steel surface obeying the Langmuir adsorption isotherm. Thermodynamic activation parameters such as activation energy, enthalpy (ΔH*), and entropy (ΔS*) of activation for corrosion process were calculated and discussed. The results obtained show that both chemical and physical adsorption of inhibitor molecules occur simultaneously and the fruit extract of shahjan (Moringa oleifera) could serve as an effective inhibitor of the corrosion of mild steel in hydrochloric acid media.     

Corrosion Investigation of Chromium Nitride and Chromium Carbide Coatings for PEM Fuel Cell Bipolar Plates in Simulated Cathode Condition

Transition metals nitrides and carbides are used as coatings on bipolar plates for proton exchange membrane fuel cells (PEMFCs) due to their suitable electrical conductivity and corrosion resistance. Chromium electroplated AISI 316L stainless steel bipolar plates were treated by plasma nitriding and solid carburizing to form chromium nitride and chromium carbide, respectively. The presence of CrN/Cr₂N and Cr₇C₃/Cr₂₃C₆ was verified by X‐ray diffractometry (XRD) in chromium nitride and chromium carbide coatings, respectively. The corrosion behavior of coatings was investigated by potentiodynamic polarization, potentiostatic polarization and electrochemical impedance spectroscopy (EIS) in simulated cathode condition. Coated samples showed better corrosion behavior than untreated bare sample. EIS results indicated decrease in corrosion current density after 500 hours, however coatings acted as barrier against solution access to substrate. Corrosion current densities of coatings were close to targets of United Stated department of energy (DOE).     

Corrosion behavior of two bipolar plate materials in simulated PEMFC environment by electrochemical noise technique

The corrosion behavior of 316L stainless steel (316L) and bulk amorphous Zr₇₅Ti₂₅ (AB) alloy was studied using electrochemical noise (EN) in simulated polymer electrolyte membrane fuel cell (PEMFC) conditions at 25 and 80 °C. At open circuit potential, under H₂ environment, AB exhibited a higher corrosion-resistance than 316L and the contrary was observed under O₂ environment. At imposed cathodic potential, under H₂ environment for PEMFC anodic simulation, the reduction mechanism of 316L at 80 °C gave the most important EN signals of all other conditions. At imposed anodic potential, under O₂ environment for cathodic simulation, the passive state was observed for 316L while severe localized corrosion for AB was obvious at 80 °C. It is concluded from the corrosion data of this work that in the anode environment of a PEMFC, the AB alloy could be a better candidate than 316L for bipolar plates. The contrary was observed in the simulated cathode environment.     

Classic and local analysis of corrosion behaviour of graphite and stainless steels in polluted phosphoric acid

In phosphoric acid solution (40% H₃PO₄), the corrosion behaviour of graphite and stainless steels was studied by the use of different electrochemical methods, namely polarization curve analysis, electrochemical impedance spectroscopy (EIS) and scanning vibrating electrode technique (SVET). The combined effect of chemical impurities and the increase of medium temperature was studied to approach the real conditions in the process of phosphoric acid manufacturing. It was found that the current density measured by polarization curves increased with the presence of chloride and sulphate ions in the acid solution whatever the tested material. Compared to stainless steels, graphite had the best corrosion resistance in polluted phosphoric acid. However, for graphite the increase of temperature from 20 to 80 °C induced an increase of the corrosion rate and potential and a decrease of the resistance confirmed by EIS results. Subsequently, local currents were detected at the surface of the sample by using the scanning vibrating electrode technique. From the data obtained, graphite surface manifested a distinctive behaviour from that of stainless steels. A generalized corrosion was occurred on graphite whereas a localized corrosion was observed for stainless steels. These results show a clear interest of graphite as component material in some of the equipments of the phosphoric acid industry.     

Electrochemical corrosion properties of metal alloys used in orthopaedic implants

This study concerns an investigation of the corrosion behavior of 316 stainless steel, CoCrMo and Ti6Al4V alloys in simulated body conditions (ringer lactate) at 37 °C by the use of Tafel plots, mixed potential and electrochemical impedance spectroscopy (EIS). Ti6Al4V alloy has the highest corrosion resistance followed by CoCr alloy. Ti6Al4V–CoCrMO was the best couple for galvanic corrosion with the minimum galvanic potential and current values according to mixed potential theory and Tafel method. It was concluded that Ti6Al4V was the most suitable material for implant applications in the human body.     

Corrosion inhibition performance of 2-mercaptobenzimidazole and 2-mercaptobenzoxazole compounds for protection of mild steel in hydrochloric acid solution

The effect of some mercapto functional azole compounds on the corrosion of mild steel in 1 M hydrochloric acid solution was studied by polarization and electrochemical impedance spectroscopy (EIS). Polarization studies showed depression of cathodic and anodic polarization curves in the presence of mercapto functional azole compounds, indicating mixed type corrosion inhibition of the compounds. Double layer capacitance and charge transfer resistance values were derived from EIS results. Changes in impedance parameters are indicative of adsorption of these compounds on the metal surface. Surface analysis SEM/EDX showing presence of sulfur on the surface confirmed the adsorption of the azole compounds on the mild steel surface as showed by electrochemical methods. Both compounds contain a pyridine-like nitrogen atom and a sulfur atom in their molecular structure, while they differ in only one heteroatom: oxygen in the oxazole ring and pyrrole-like nitrogen in the imidazole ring. The results of the electrochemical techniques revealed that changing the pyrrole like nitrogen atom to oxygen atom in the azole ring results in a decrease of corrosion inhibition performance in hydrochloric acid solution, which could be related to more negative charge on pyrrole-like nitrogen atom in comparison to oxygen atom as depicted by quantum chemical calculations.     

油酸咪唑啉类缓蚀剂对不锈钢的缓蚀性能研究

利用静态失重法、Tafel极化曲线研究了油酸咪唑啉类缓蚀剂在不同酸介质中对不锈钢的缓蚀性能,并尝试了油酸咪唑啉缓蚀剂与KI的复配实验。结果表明,油酸咪唑啉类缓蚀剂在10%盐酸中和10%硫酸中对不锈钢有很好的缓蚀作用。在10%盐酸介质中,只需加入0.3%的油酸咪唑啉缓蚀剂,不锈钢材质的缓蚀率就能达到98%;在10%硫酸介质中,缓蚀率在油酸咪唑啉缓蚀剂添加量为0.5%时最大,达到94%。与KI的复配结果表明,咪唑啉与KI之间有一定的缓蚀协同效应,复合使用可以达到降低成本和保持高缓蚀率的作用。     

Corrosion protection of mild steel by polyvinylsilsesquioxanes coatings in 3% NaCl solution

Polyvinylsilsesquioxanes (PVS) coatings were synthesized by the hydrolytic polycondensation of vinyltrimethoxysilane using hydrochloric acid as a catalyst. Their structure was characterized by Fourier transform IR (FTIR) and the viscosity [in centipoise(cP)] of polyvinylsilsesquioxanes was measured at 298 K. The electrochemical behavior of I–IV coated steel electrodes, of polymer concentration as follows: [I(20%), II(40%) of viscosity 50 cP and III(20%), IV(40%) of viscosity 15 cP], was investigated in 3% NaCl solution using various electrochemical techniques, i.e., open-circuit potential (OCP), potentiodynamic polarization, electrochemical impedance measurements (EIS), and surface examination via scanning electron microscope (SEM) technique. The influence of immersion time on the electroctrochemical behavior of polysilsesquioxane-coated electrodes was also studied. The results of polarization measurements showed that corrosion current density (i _corr) decreases in the order IV > III > II > I. Also, the film resistance is the highest for PVS-coated electrode I as evaluated from EIS measurements. OCP, EIS, and polarization results are in good agreement with each other. The obtained results were confirmed by surface examination using scanning electron microscope.     

Corrosion resistance of poly p-phenylenediamine conducting polymer coated 316L SS bipolar plates for Proton Exchange Membrane Fuel Cells

The usage of conducting polymers as coating materials for bipolar plates to prevent corrosion is the recent trend in Proton Exchange Membrane Fuel Cell (PEMFC) technology. Paraphenylenediamine (pPD) monomer was electropolymerized to poly p-phenylenediamine (PpPD) over 316L SS. The characterization of PpPD, the conducting polymer coating, over 316L SS was done using attenuated total reflectance infra-red (ATR-IR) spectroscopy to confirm the formation of PpPD. The surface morphology and topography were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion protection performance of the coating was evaluated using open circuit potential (OCP) measurement, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization studies in PEMFC environment. EIS studies revealed that the charge transfer resistance for the coated substrates has increased by one order of magnitude than the bare substrate. Potentiodynamic polarization studies have registered lower corrosion current density by one order magnitude for the 0.06 M pPD coated substrate than the bare substrate and the polarization resistance values for the coated substrates have increased by two and a half time than the bare substrate. These results showed that PpPD coated substrates exhibited enhanced corrosion resistance in PEMFC environment.     

Effect of sub-layer temperature during HFCVD process on morphology and corrosion behavior of tungsten carbide coating

WC coating was deposited on the polished and cleaned 316L stainless steel by Hot Filament Chemical Vapor Deposition (HFCVD) technique at 400°C and 500°C. Field Emission Gun Scanning Electron Microscope (FEG-SEM) was used to study the corrosion morphology of the WC coatings. Energy dispersive spectroscopy (EDS) was used to analyze the chemical composition of the coatings. Coating porosity was measured by immersion in water. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques were used to study the corrosion behavior of the coating in the solution of 1 mol/L H₂SO₄. Results showed that the WC coatings have a honeycomb microstructure where its porosity was increased at higher temperature of the sub-layer. Also, the WC coating significantly increases the corrosion resistance of 316L stainless steel. And increasing the sub-layer temperature in the HFCVD method reduces the corrosion resistance of the WC coating. Corrosion morphology was indicative of pitting corrosion of the WC coating.     

Evaluation of the corrosion resistance of Ni-Co-B coatings in simulated PEMFC environment

The corrosion resistance behavior of Ni-Co-B coated carbon steel, Al 6061 alloy and 304 stainless steel was evaluated in simulated proton exchange membrane fuel cell (PEMFC) environment. The phase structure of the NiCoB based alloy was determined by Rietveld analysis. The PEMFC environment was constituted of 0.5 M H₂SO₄ at 60 °C and the evaluation techniques employed included potentiodynamic polarization, linear polarization resistance, open circuit potential measurements and electrochemical impedance spectroscopy. The results showed that in all cases the corrosion resistance of the Ni-Co-B coating was higher than that of the uncoated alloys; about two orders of magnitude with respect to carbon steel and an order of magnitude compared to 304 stainless steel. Except for the uncoated 304 type stainless steel, the polarization curves for the coated specimens did not exhibit a passive region but only anodic dissolution. The corrosion potential value, E_corr, was always nobler for the coated samples than for the uncoated specimens. This was true for the stainless steel in the passive region, but in the active state for the carbon steel and Al 6061 alloy. The corrosion of the underlying alloy occurred due to filtering of the solution through coating defects like microcracks, pinholes, etc. During the filtering process the E_corr value of the coating decreased slowly until it reached a steady state value, close to the E_corr value of the underlying alloy.     

THE ROLE OF PHOSPHONATE DERIVATIVES ON THE CORROSION INHIBITION OF STEEL IN HCL MEDIA

The inhibition of corrosion of steel by two P-containing compounds, sodium methyldodecyl phosphonate and sodium methyl (11-smethacryloyloxyundecyl) phosphonate, in hydrochloric acid has been investigated at various temperatures using electrochemical techniques (impedance spectroscopy (EIS), potentiodynamic polarization) and weight loss measurements. Inhibition efficiency (E%) increased with phosphonate concentration. Adsorption of inhibitors on the steel surface in 1 M HCl follows the Langmuir isotherm model. EIS measurements showed that the dissolution process of steel occurred under activation control. Polarization curves indicated that inhibitors tested acted as cathodic inhibitors. The temperature effect on the corrosion behavior of steel in 1 M HCl without and with the inhibitor was studied in the temperature range from 313 to 353 K. The adsorption free energy and activation parameters for the steel dissolution reaction in the presence of phosphonates were determined.     

THE ROLE OF PHOSPHONATE DERIVATIVES ON THE CORROSION INHIBITION OF STEEL IN HCL MEDIA

The inhibition of corrosion of steel by two P-containing compounds, sodium methyldodecyl phosphonate and sodium methyl (11-smethacryloyloxyundecyl) phosphonate, in hydrochloric acid has been investigated at various temperatures using electrochemical techniques (impedance spectroscopy (EIS), potentiodynamic polarization) and weight loss measurements. Inhibition efficiency (E%) increased with phosphonate concentration. Adsorption of inhibitors on the steel surface in 1 M HCl follows the Langmuir isotherm model. EIS measurements showed that the dissolution process of steel occurred under activation control. Polarization curves indicated that inhibitors tested acted as cathodic inhibitors. The temperature effect on the corrosion behavior of steel in 1 M HCl without and with the inhibitor was studied in the temperature range from 313 to 353 K. The adsorption free energy and activation parameters for the steel dissolution reaction in the presence of phosphonates were determined.     

不锈钢金属双极板TiW和TiTa膜的制备及性能

针对质子交换膜燃料电池金属双极板耐蚀性和导电性有待提高的问题,本文用磁控溅射双靶共溅的方法,在316L不锈钢基体表面沉积TiW和TiTa两种非贵金属膜层。通过X射线衍射、扫描电子显微镜-能谱仪、X射线光电子能谱仪、电化学和接触电阻测试等方法,表征了涂覆膜层后不锈钢的微观结构、表面形貌、化学组成、耐腐蚀性和导电性。实验结果表明,磁控溅射制备得到的TiTa膜表面较为均匀,且TiTa膜沉积的不锈钢具有较好的耐腐蚀性,其恒电位极化电流密度能够维持在0.3μA/cm²;从导电性来看,TiW膜与碳纸之间的接触电阻小于TiTa膜。综合考虑材料的各项性能,认为沉积TiTa膜的316L不锈钢有用作金属双极板材料的潜力。     

Localized corrosion of carbon steel in a CO2-saturated oilfield formation water

In this work, corrosion and localized corrosion behavior of X65 pipeline steel were studied in a simulated, CO₂-saturated oilfield formation water by various electrochemical measurement techniques, including electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curves, galvanic current and localized EIS (LEIS). The morphology and composition of the formed corrosion scale were characterized by scanning electron microscopy and energy-dispersive X-ray analysis. A conceptual model was developed to illustrate the occurrence of localized corrosion of the steel under scale. Both galvanic current and LEIS measurements showed that a galvanic effect existed between the bare steel and the scale-covered region. The scale-covered region served as cathode and the bare steel site as the anode. The big cathode vs. small anode geometry accelerated the local corrosion reaction. At an elevated temperature, a compact, crystalline scale was formed on the steel surface, enhancing the galvanic effect. Moreover, the stability of the scale was increased with time, and localized corrosion of the steel under scale experienced mechanistic changes with time.     

类金刚石薄膜在模拟体液中的电化学阻抗

利用双放电腔微波等离子体源全方位离子注入设备,分别采用等离子体增强化学气相沉积技术、等离子体源离子注入和等离子体增强化学气相沉积复合技术两种工艺对医用3161,不锈钢进行类会刚石薄膜表面改性。利用电化学阻抗谱法考察了两种工艺制备的类金刚石薄膜在模拟体液中的抗腐蚀性能。结果表明：与采用等离子体增强化学气相沉积技术制备的类金刚石薄膜相比,在72h的浸泡时间内,采用等离子体源离子注入和等离子体增强化学气相沉积复合技术制备的类金刚石薄膜防腐蚀性能明显增高,腐蚀阻抗较高,碳注入层可有效抑制溶液渗入薄膜和基体之间的界面,起到了腐蚀防护层的作用。动电位极化测试表明：采用复合技术制备的类金刚石薄膜在模拟体液中的腐蚀倾向性更低,钝态稳定性更好。