Application of polyaniline to galvanic anodic protection on stainless steel in H2SO4 solutions

A stand-alone polyaniline (PANI) film electrode was made and then applied to protect 1Cr13 stainless steel (a type of stainless steel typically used in China, 0–15% C, 13% Cr) from corrosion in highly acidic solution, up to 5 M H₂SO₄. The stand-alone PANI electrode and 1Cr13 were coupled to study their galvanic interactions. PANI is a cathode while 1Cr13 is an anodic. The results indicate that PANI with a certain area can quickly passivate the stainless steel and effectively maintain the steady passive state for a long period of time. This specific method of PANI preventing 1Cr13 from corrosion is called galvanic anodic protection (GAP). Moreover, the efficiency, mechanism, and security of GAP were discussed. The results demonstrate that the stand-alone PANI electrode may have a potential application to galvanic anodic protection on stainless steel in highly corrosive H₂SO₄ solutions.     

Corrosion protection of stainless steel by separate polypyrrole electrode in acid solutions

Galvanic anodic protection (GAP) of stainless steels by doped polypyrrole (PPy) was investigated using chemically synthesized PPy. Separate PPy powder‐pressed electrodes with different surface areas were prepared. Electrochemical properties of PPy electrodes were studied by open circuit potentials (OCPs) and potentiostatic polarization. PPy powder‐pressed electrodes were coupled with 410‐stainless steel electrodes in different concentrations of sulfuric acid solutions, 5 M phosphoric acid solution, and industrial phosphoric acid solution (5 M phosphoric acid + 0.05% chloride ion). Remarkable shift of OCP to the positive direction and sharp decrease of corrosion rate were observed during the coupling experiments, which implies that 410‐stainless steel was transferred to passive state. Results also showed that PPy electrode with sufficient surface area can provide corrosion protection to 410‐stainless steel electrode in highly corrosive acid solution. Based on the experiment results, GAP provided by PPy and PANi (synthesized under similar conditions) was compared.     

Effect of chloride ions on corrosion behaviour of austenitic nickel and nickel free stainless steels in phosphoric acid solutions

The effect of chloride ions' presence (0·005–1·0M NaCl) in phosphoric acid solutions (5, 40 and 75%) on the corrosion behaviour of three austenitic stainless steels (an experimental steel Fe–18Cr–12Mn–0·6N and two trade grades, Fe–18Cr–9Ni and Fe–14Cr–15Mn–0·2N) has been studied by potentiodynamic polarisation measurements. The surface examinations of the samples tested involved X-ray photoelectron spectroscopy as well as optical and scanning electron microscopy. It was established that chlorides added to phosphoric acid solutions deteriorate the general corrosion resistance, and under anodic polarisation, they provoke pitting corrosion. The composition of the stainless steels significantly influences its corrosion behaviour in the phosphoric acid solutions containing chloride ions. The replacement of nickel with manganese and nitrogen on top of lower chromium content has a strong negative effect on the corrosion resistance.     

Corrosion rate of construction materials in hot phosphoric acid with the contribution of anodic polarization

The paper is focused on selection of a proper material for construction elements of water electrolysers, which make use of a 85% phosphoric acid as an electrolyte at temperature of 150 °C and which might be loaded with anodic polarization up to 2.5 V versus a saturated Ag/AgCl electrode (SSCE). Several grades of stainless steels were tested as well as tantalum, niobium, titanium, nickel alloys and silicon carbide. The corrosion rate was evaluated by means of mass loss at free corrosion potential as well as under various levels of polarization. The only corrosion resistant material in 85% phosphoric acid at 150 °C and at polarization of 2.5 V/SSCE is tantalum. In that case, even a gentle cathodic polarization is harmful in such an acidic environment. Hydrogen reduction leads to tantalum hydride formation, to loss of mechanical properties and to complete disintegration of the metal. Contrary to tantalum, titanium is free of any corrosion resistance in hot phosphoric acid. Its corrosion rate ranges from tens of millimetres to metres per year depending on temperature of the acid. Alloy bonded tantalum coating was recognized as an effective corrosion protection for both titanium and stainless steel. Its serviceability might be limited by slow dissolution of tantalum that is in order of units of mm/year.     

镁合金在大气环境中电偶腐蚀行为及规律的研究

在北京大气环境下，研究AM60镁合金和不同金属材料（碳钢、不锈钢、黄铜和铝合金）偶接的电偶腐蚀行为规律。研究表明，镁合金作为阳极发生不同程度的电偶腐蚀，通过1a的北京大气环境下的暴露试验后，AM60镁合金的电偶腐蚀效应由强到弱的顺序为：碳钢、黄铜、不锈钢和铝合金，其中镁合金与LY12铝合金偶接的电偶腐蚀效应最小。通过与其它地区室外暴晒的镁合金电偶腐蚀效应的对比，表明环境因素影响着镁合金的电偶腐蚀效应。同时阴极材料、试验时间、试样尺寸（偶接面积）和试验环境都会对镁合金电偶腐蚀效应产生影响。经1a曝晒的AM60镁合金形成了具有保护性的腐蚀产物层阻碍了腐蚀发展。北京地区高自然降尘量导致金属表面湿润时间加大，从而加速了AM60镁合金的电偶腐蚀。采用XRD方法分析表面的腐蚀产物，用金相显微镜和扫描电镜（SEM）观察试样腐蚀后的表面形貌特征和腐蚀产物的结构，并用与之相连的能谱仪分析腐蚀产物中的元素组成。     

CO2环境下油酸咪唑啉对X65钢异种金属焊缝电偶腐蚀的抑制作用研究

研究了X65管线钢与316L不锈钢、Inconel 625双金属复合管的异种金属焊缝在CO2环境下的电偶腐蚀行为,以及油酸咪唑啉的缓蚀作用。结果表明,随着电偶电位差的增大,异种金属焊缝的腐蚀速率明显升高,并且都显著高于母材。添加油酸基咪唑啉缓蚀剂能降低异种金属焊缝在CO2环境下的均匀腐蚀速率。但是,当缓蚀剂浓度添加较低时,异种金属焊接试样的碳钢一侧出现了严重的沟槽腐蚀或密集的点蚀坑;进一步增加缓蚀剂浓度才能消除沟槽腐蚀现象。讨论了缓蚀剂对异种金属焊缝电偶腐蚀的抑制机理,该项研究可为异金属焊接接头处的腐蚀防护提供借鉴。     

Polyaniline coating on 304 stainless steel by electropolymerisation from aqueous NaOH solution for corrosion protection in NaCl medium

Abstract

Polyaniline (PAn) coating was electrochemically synthesised on 304 stainless steel using cyclic voltammetry in 0·25M NaOH solution containing 0·1M aniline. Characterisation of the adhesive and stable PAn coating was carried out by cyclic voltammetry, Fourier transform infrared spectroscopy and scanning electron microscopy. The protective properties of PAn coating on 304 stainless steel were elucidated using linear anodic potentiodynamic polarisation and Tafel test in 3·5%NaCl solution. Linear anodic potentiodynamic polarisation test results proved that the PAn coating improved the degree of protection against pitting corrosion in NaCl solutions. Tafel test results showed that the PAn coating appeared to enhance protection for 304 stainless steel in 3·5%NaCl solution.     

Prevention of transpassive dissolution of austenitic stainless steel counter electrodes in nickel based electrolytic coloring solutions for anodized aluminum

In low nickel ion containing, weak acidic, electrolytic coloring solutions for anodized aluminium, austenitic stainless steel counter electrodes dissolve transpassively. The role of nickel and cobalt ions in preventing the transpassive dissolution of AISI Type 304 and 316 austenitic stainless steel counter electrodes was investigated. Potantiodynamic polarization method was used. The test solutions were a buffer (29.66 g/lt boric acid), a buffered supporting electrolyte (32.6 g/lt boric acid + 26.18 g/lt magnesium sulphate heptahydrate + 14,95 g/lt ammonium sulfate) and the coloring solutions (supporting electrolyte with different nickel (27.6–101 g/lt as heptahydrated sulfate) and cobalt (33–166 ppm) content). The oxidation of bivalent nickel ions starts 200 mV lower than the transpassive dissolution of stainless steel. However, even a small amount of cobaltous ions (165 ppm) in the solution produces a much steeper oxidation peak on the top of the nickel oxidation current. In order to transpassively dissolve a stainless steel electrode in cobalt containing nickel solutions, anodic current must be greater than the combined oxidation peak of nickel and cobalt ions, otherwise the working potential of the stainless steel electrode is always kept at the passive region hence the transpassive dissolution is prevented.     

Corrosion characteristics of composite/metallic material couples

Abstract

The galvanic corrosion induced by graphite/epoxy composite materials (GECMs) on coupled metallic materials (ferrous and non-ferrous) in neutral, air saturated aqueous 3·5%NaCl solutions has been investigated. Two types of composite, manufactured by Fiberite and Ciba Geigy, were used, electrically coupled to the aluminium alloys 2024–T3, 7075–T6, 7075–T73, and 5052 and the stainless steels 301 1/2 H, 302 1/4 H, 321, 15–5–PH, and 17–7–PH. Galvanic currents were measured using a zero resistance ammeter for different values of cathodic/anodic area ratio in 24 h tests. The galvanic current was independent of anodic area and directly proportional to the cathodic area for, the aluminium alloys, while a dependence on both anodic and cathodic areas was found for the stainless steels investigated. These results are. in good agreement with theoretical computation based on mixed potential theory.     

不锈钢包钢在红壤中的电偶腐蚀行为

通过失重法、电化学方法研究了不锈钢包钢在红壤中的电偶腐蚀行为,采用SEM、XRD观察分析试样的表面形貌及腐蚀产物。结果表明:不锈钢-碳钢电偶对的形成加速了阳极金属材料的腐蚀,随着电偶对阴阳极面积比的增加,电偶电流逐渐增大;不锈钢在浸泡45d后基本没有发生腐蚀,而碳钢则发生了极严重的全面腐蚀,腐蚀产物主要为铁的氧化物。     

Corrosion resistance of PANi‐coated steel in simulated PEMFC anodic environment

By using electrochemical techniques, the corrosion resistance of polyaniline (PANi)‐coated 1Cr18Ni9Ti stainless steel was investigated in simulated proton exchange membrane fuel cell (PEMFC) anodic environment. The results indicated that the compact conductive PANi film could be obtained on 1Cr18Ni9Ti steel by pulse potentiostatic method (PPSM). When steel was coated with conductive PANi, its corrosion potential was improved from ?350 to 250 mV in simulated corrosion solution. During the potentiostatic polarization in PEMFC's anodic operation environment, the film is stable and there is no degradation of the PANi film. The film has no effect on the performance of the fuel cell. Further effort to improve the performance of conductive polymer coatings and to estimate the long‐term performance in actual PEMFC environment is desirable.     

Effect of aqueous LiBr solutions on the corrosion resistance and galvanic corrosion of an austenitic stainless steel in its welded and non-welded condition

The corrosion resistance and galvanic behaviour of a highly alloyed austenitic stainless steel (UNS N08031) and a nickel-base alloy (UNS N06059) in its welded (GTAW) and non-welded condition were analysed in LiBr solutions by means of electrochemical measurements. Samples microstructure was studied by SEM and EDX analysis. The alloys considered showed passive behaviour and they were able to repassivate after the breakdown of the passive film. The pitting resistance of the materials increased as the LiBr concentration decreased. With regard to galvanic corrosion, the welded metal was always the anodic element of the UNS N08031-welded metal pair.     

Poly(ortho-ethoxyaniline) in corrosion protection of stainless steel

Corrosion protection of stainless steel (13% Cr) coated with poly(ortho-ethoxyaniline) (POEA) has been investigated. The layers of POEA were synthesised from sulphuric and phosphoric acid solutions by means of cyclic voltammetry. The protecting properties of the layers in supporting electrolytes were investigated by monitoring the open circuit potential (E_oc) vs. time, and by electrochemical impedance spectroscopy (EIS). It was found that polymer layers provide corrosion protection, i.e. they help to stabilise the potential of the metal in the passive potential region. The protective properties of POEA layers have shown to be superior to polyaniline (PANI) layers, which is explained by a denser morphology of POEA. The behaviour of POEA obtained on stainless steel, examined by EIS, is different from the one obtained for POEA on Pt electrode. The registered resistance in the case of POEA on stainless steel represents the charge transfer resistance at polymer/solution interface, i.e. the polymer resistance. These measurements show that a part of the layer is reduced, i.e. that there is an interaction between polymer layer and stainless steel. EIS measurements prove the influence of monomer on stainless steel oxide formation and suggest that polymer is partly incorporated into the oxide film.     

Corrosion, passivation and breakdown of passivity of neodymium

The anodic polarisation behaviour of neodymium was investigated in various solutions (pH 1-12). While in sulphuric acid solution high dissolution rates were observed, spontaneous passivity occurred in phosphoric acid solutions, oxalic acid solutions and sodium hydroxide solutions. However, the stability of these protecting layers strongly depends on the kind and concentration of anions present, especially in acidic environments. A mechanism of the passive layer breakdown is proposed. During pitting corrosion erosive degradation of the electrode was observed. In all solutions, abnormal hydrogen evolution was observed when neodymium was in the active state during anodic polarisation.     

Poly(N-methylaniline) coatings on stainless steel by electropolymerization

Poly(N-methylaniline) (PNMA) coatings have been electropolymerized on 304 stainless steel alloy by potentiodynamic, galvanostatic and potentiostatic synthesis techniques from aqueous solutions of 0.1 M N-methylaniline (NMA) and 0.3 M oxalic acid. Characterization of PNMA coatings was carried out by cyclic voltammetry, UV-Vis and FTIR spectroscopy techniques. Corrosion behavior of PNMA coated stainless steel electrodes was investigated using linear anodic potentiodynamic polarization, Tafel test, chronoamperometry and electrochemical impedance spectroscopy (EIS) techniques in 0.5 M aqueous HCl solutions. Corrosion test results showed that PNMA coatings possessed protection to uncoated stainless steel against corrosion.     

The Effect of Products of Nitrate Ion Reduction on the Kinetics of Electrode Reactions on Stainless Steel

The effects of nitrate ions and possible products of their reduction (ammonium, hydrazine, and hydroxylammonium ions) on electrochemical characteristics of stainless steel are studied in phosphoric acid. Specific properties of nitrates as corrosion inhibitors of a passivating type are explained by a complex effect of their reduction products on the kinetics of both cathodic and anodic reactions. It is found that the products of nitrate reduction, firstly, accelerate cathodic reactions, secondly, accelerate anodic reactions due to the formation of complexes with the ions of corroding steel, and, thirdly, reducte passivation potential due to alkaline properties of certain products. Everything aforementioned substantially affects the possibility of using nitrates as the corrosion inhibitors of stainless steel in acidic media.     

Laboratory Studies of Galvanic Corrosion – II. Three-metal Couples

Electrochemical and weight loss measurements have been used to study galvanic corrosion of three-metal couples extending earlier studies of the galvanic interaction of two dissimilar metals. Materials studied include Zn, Cd, Cu, Ni, the Al alloys 2024, 6061 and 7075, 4130 steel, stainless steel 304, Ti-6Al-4V, Inconel 718 and Haynes 188 in 3.5% NaCl at 21°C. Different electrical arrangements for galvanic current measurements using the zero resistance ammeters (ZRA) are discussed. With the use of two ZRA's the current flowing on each of three metals can be continuously monitored. Weight loss data are used to obtain additional information concerning accelerated corrosion or protection of the individual metals in galvanic couples. Such measurements can be used to evaluate the corrosion behavior of metal combinations such as encountered in a porous Cd coating on a steel fastener installed on an Al structure.     

The synergy between deformation and anodic dissolution of an austenitic stainless steel in acidic chloride solution

In corrosion medium, metals can deform under tensile stress and form a new active surface with the anodic dissolution of the metals being accelerated. At the same time, the anodic dissolution may accelerate the deformation of the metals. The synergy can lead to crack nucleation and development and shorten the service life of the component. Austenitic stainless steel in acidic chloride solution was in active dissolution condition when stress corrosion cracking (SCC) occurred. It is reasonable to assume that the anodic dissolution play an important role, so it's necessary to study the synergy between anodic dissolution and deformation of austenitic stainless steels. The synergy between deformation and anodic dissolution of AISI 321 austenitic stainless steel in an acidic chloride solution was studied in this paper. The corrosion rate of the steel increased remarkably due to the deformation‐accelerated anodic and cathodic processes. The creep rate was increased while the yield strength was reduced by anodic dissolution. The analysis by thermal activation theory of deformation showed a linear relationship between the logarithm of creep rate and the logarithm of anodic current. Besides, the reciprocal of yield strength was also linearly dependent on the logarithm of anodic current. The theoretical deductions were in good agreement with experimental results.     

Corrosion and passivation mechanism of chromium diboride coatings on stainless steel

The corrosion resistance of fully crystalline CrB₂ coatings magnetron sputtered onto AISI 316L stainless steel was tested in acidic solutions. CrB₂ coatings showed excellent corrosion protection, but suffered a breakdown when an anodic potential of greater than about +1 V (SHE) was applied to the surface in a 1 M HCl electrolyte. The coating failure at high potentials is attributed to transpassive dissolution of the coating at volume defects, enabling the electrolyte to reach the underlying 316L substrate, resulting in its rapid corrosion and subsequent fracturing of the coating. Electrochemical data and potential-pH (Pourbaix) diagrams, constructed from thermodynamic data, indicate that the corrosion resistance of CrB₂ is due to the formation of a Cr(III) oxide passive film in the absence of activation corrosion.     

Galvanic corrosion of bare and coated Al alloys coupled to stainless steel 304 or Ti-6Al-4V

The galvanic corrosion behavior of Al alloys 7075, 6061, 2024, bare or coated with the chemical conversion coating Alodine 600, coupled to stainless steel 304 or Ti-6Al-4V and immersed in aerated 3·5%NaCl solution, has been studied by continuous measurements of the galvanic current using a zero impedance ammeter and by weight loss measurements. Comparison of weight loss measurements for bare and coated uncoupled Al alloys shows that good corrosion protection is provided by the conversion coating. Data from weight loss and galvanic current measurements show that corrosion protection is also provided when coated Al alloys are coupled to stainless steel 304 or Ti-6Al-4V. Examination of potentiostatic polarization curves for the metals studied in 3·5%NaCl solution explains the protective action of the coating and also the higher dissolution rates of Al alloys coupled to stainless steel 304 instead of Ti-6Al-4V. Differences between dissolution rates calculated from galvanic current data and weight loss data are explained by theoretical considerations published recently by the authors taking into account the shapes of the individual polarization curves of the metals in the couple. After correction of galvanic current data, agreement between dissolution rates obtained by weight loss and galvanic current data is satisfactory. Continuous recording of the galvanic current reveals considerably more information than weight loss data.