Studies on corrosion inhibition of steel reinforcement by phosphate and nitrite

This work deals with the effectiveness of sodium phosphates and nitrites used as inhibitors against steel corrosion in concrete reinforcement. First, concrete pore water was simulated with several alkaline solutions. Then, reinforced concrete specimens with inhibitors added in fresh concrete mix are immersed in chloride solution. The effectiveness of inhibitors was assessed by applying electrochemical techniques, namely Electrochemical Impedance Spectroscopy (EIS), Polarisation Curves (PC), and Open Circuit Potential (OCP) measurements. The final concrete condition was analysed with Scanning Electronic Microscopy (SEM), X-Ray Diffraction (XRD) and Infrared Spectroscopy (FT-IR).In solutions simulating concrete contaminated with chloride, the influence of the inhibitors on the steel corrosion was assessed by (PC) and (EIS). The results obtained show that phosphate prevents pitting corrosion when its content is equal to chloride concentration, and that nitrite only contributes to increase the value of pitting potential. Corrosion rate is reduced with both inhibitors at the different contents tested.For reinforced concrete specimens immersed in chloride solution, their conditions were assessed by applying EIS. The results indicate that after 1 year of immersion with the two inhibitors the corrosion rate decreased. Then, after 3 years of immersion no influence of inhibitors on the corrosion rate was observed. However a significant increase in concrete electrical resistance was observed when inhibitors were present. Visual examinations showed that all steel bars were corroded in the presence of chlorides.Results from analytical tests done on the concrete after 3 years of immersion show that as far as the final concrete condition is concerned, the tested inhibitors did not change the type of compounds in concrete. But the final free chloride content remained higher than the critical chloride threshold. The results of FT-IR technique showed that nitrites are likely washed out of concrete during immersion in chloride solution and phosphates interfere with the equilibrium between CO₃ ^2? and HCO₃ ^? in concrete.The main conclusion of this study is: the efficiency of the tested inhibitors decreases with time, after two years of immersion in chloride solution.     

Effect of zinc phosphate chemical conversion coating on corrosion behaviour of mild steel in alkaline medium: protection of rebars in reinforced concrete

We outline the ability of zinc phosphate coatings, obtained by chemical conversion, to protect mild steel rebars against localized corrosion, generated by chloride ions in alkaline media. The corrosion resistance of coated steel, in comparison with uncoated rebars and coated and uncoated steel rebars embedded in mortar, were evaluated by open-circuit potential, potentiodynamic polarization, cronoamperometry and electrochemical impedance spectroscopy. The coated surfaces were characterized by x-ray diffraction and scanning electron microscopy. First, coated mild steel rebars were studied in an alkaline solution with and without chloride simulating a concrete pore solution. The results showed that the slow dissolution of the coating generates hydroxyapatite Ca₁₀(PO₄)₆(OH)₂. After a long immersion, the coating became dense and provided an effective corrosion resistance compared with the mild steel rebar. Secondly, the coated and uncoated steel rebars embedded in mortar and immersed in chloride solution showed no corrosion or deterioration of the coated steel. Corrosion rate is considerably lowered by this phosphate coating.     

Effect of zinc phosphate chemical conversion coating on corrosion behaviour of mild steel in alkaline medium: protection of rebars in reinforced concrete

Abstract

We outline the ability of zinc phosphate coatings, obtained by chemical conversion, to protect mild steel rebars against localized corrosion, generated by chloride ions in alkaline media. The corrosion resistance of coated steel, in comparison with uncoated rebars and coated and uncoated steel rebars embedded in mortar, were evaluated by open-circuit potential, potentiodynamic polarization, cronoamperometry and electrochemical impedance spectroscopy. The coated surfaces were characterized by x-ray diffraction and scanning electron microscopy. First, coated mild steel rebars were studied in an alkaline solution with and without chloride simulating a concrete pore solution. The results showed that the slow dissolution of the coating generates hydroxyapatite Ca₁₀(PO₄)₆(OH)₂. After a long immersion, the coating became dense and provided an effective corrosion resistance compared with the mild steel rebar. Secondly, the coated and uncoated steel rebars embedded in mortar and immersed in chloride solution showed no corrosion or deterioration of the coated steel. Corrosion rate is considerably lowered by this phosphate coating.     

The influence of the surface finishing on the electrochemical behaviour of austenitic and superaustenitic steels

The influence of surface roughness on the pitting potential and the corrosion potential of the DIN W.Nr. 1.4541 and DIN W.Nr 1.4465 stainless steels were examined using electrochemical techniques. Roughness and electrochemical tests were performed on samples with various surface finishing. Electrochemical studies were conducted in an electrochemical cell where steel electrodes were immersed in 0.1 M NaCl and 0.1 M NaCl + 0.1 M Na₂SO₄ aqueous solutions. We found for both materials when immersed in 0.1 M NaCl aqueous solution lower pitting potential than in 0.1 M NaCl + 0.1 M Na₂SO₄. The results showed that the electrochemical behaviour of the DIN W.Nr. 1.4465 is better than of DIN W.Nr. 1.4541.     

S2O2-3对DP980高强钢在NaCl水溶液中的点蚀行为的影响

钢是一种冷轧双相高强度结构钢,成本低且具备良好的强度和塑性,在海工领域有巨大的潜在应用价值,但其在苛刻海水环境下的耐腐蚀性能,尤其是耐点蚀等局部腐蚀的能力有待深入研究.本文采用动电位极化法对DP980高强钢在含S₂O₃^2-离子的NaCl水溶液中的点蚀行为进行了研究,结果发现：在纯硫代硫酸钠水溶液中,DP980高强钢不发生点蚀;在不同质量分数的NaCl水溶液中,DP980高强钢发生点蚀,且随着Cl^-离子浓度的增大,DP980高强钢试样的耐点蚀性能下降明显;向NaCl溶液中加入浓度为0.001、0.01、0.1、1 mol/L的Na₂S₂O₃时,DP980高强钢试样的点蚀敏感性降低,点蚀受到明显抑制;随着Na₂S₂O₃浓度的升高,DP980高强钢的腐蚀主要以均匀腐蚀的形式发生;当试样浸泡在不同质量分数(0.1%、1%、10%)NaCl的1 mol/L Na₂S₂O₃溶液后,对试样表面腐蚀产物及腐蚀形貌进行扫描电镜观察及能谱分析,显示试样均发生均匀腐蚀,腐蚀产物为铁的硫化物,且未发现明显的点蚀.     

Investigation of phases and stability of solid electrolytes in the NASICON system

In order to study the phase change and stability of the NASICON structure, sodium, lithium and magnesium ions were chosen to substitute the zirconium ion at octahedral sites in the NASICON network. It was found that the zirconium ion can not be replaced by these ions. All the synthesized products are Na_1+xZr₂Si_xP_3?xO₁₂ and phosphate salts. NASICON immersed in liquid sodium at 300°C also results phosphate salt and ZrO₂. It was found that an appropriate excess of sodium phosphate in NASICON will improve the chemical stability, corrosion against sodium and mechanical properties.     

红壤土浸出液中SO42-对铜包钢耐蚀性能的影响研究

本文采用扫描电镜/能谱分析(SEM-EDS)、动电位极化、电化学阻抗谱技术研究了铜包钢接地材料受SO₄^2-浓度影响的腐蚀行为.研究结果表明在含有不同浓度的SO₄^2-的红壤土浸出液浸泡20 d,铜包钢都已出现点蚀现象.随着SO₄^2-浓度从0.05~0.2 mol/L逐渐增加,铜包钢腐蚀程度呈现先增后减弱的趋势,在0.05 mol/L的SO₄^2-浸出液中浸泡20天腐蚀最为严重,已腐蚀至内层钢.由于0.05 mol/L的SO₄^2-浸出液中腐蚀后的铜包钢表面已被较多的不导电的腐蚀产物覆盖,因此实验结果显示其阻抗值最大和腐蚀速率最慢.     

The inhibition of mild steel corrosion in hydrochloric acid media by two Schiff base compounds

Schiff bases of 2-({-1-methyl-3-[(2-sulfanylphenyl)imino]butylidene}-amino)-1-benzenethiol and 2-({-1,2-diphenyl-2-[(2-sulfanylphenyl)imino]ethylidene}amino)-1-benzenthiol are investigated as corrosion inhibitors in acid solution. Polarization, electrochemical impedance spectroscopy, and weight loss measurements were performed on mild steel in 15% HCl with and without the inhibitors. A significant decrease in the corrosion rate of mild steel was observed in the presence of investigated inhibitors. Polarization curves indicate that both compounds are mixed inhibitors, affecting both cathodic and anodic corrosion currents. The adsorption of inhibitors on mild steel surface in 15% HCl was found to follow Langmuir adsorption isotherm. Thermodynamic adsorption parameters (K _ads, ∆G _ads) of studied Schiff bases were calculated using the Langmuir adsorption isotherm. Activation parameters of the corrosion process such as activation energies, E _a, activation enthalpies, ∆H*, and activation entropies, ∆S*, were calculated by the obtained corrosion currents at different temperatures.     

The effect of phosphate ions on the electrochemical behaviour of brass in sulphate solutions

In this study, we have investigated the effect of phosphate ions on the corrosion behaviour of brass in 0.1 M Na₂SO₄ solution in acidic (pH 2.1), neutral (pH 7.2) and alkaline (pH 12.3) solutions. For this purpose, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) techniques were used. The surface morphology of the metal surface after exposed to corrosive medium was investigated by scanning electron microscopy (SEM). The effect of temperature has also studied in the temperature range from 293 K to 353 K. Some thermodynamic parameters were calculated and discussed. It was found that, PO₄^3? ions could inhibit the corrosion of brass in Na₂SO₄ solution. However, the inhibition efficiency decreased with increasing temperature. The inhibition effect of PO₄^3? ions was explained by complex formation between phosphate ions and corrosion products which physically adsorbed on the metal surface.     

含H2S的NaCl溶液中溶解氧对PH13-8Mo钢腐蚀性能的影响

为研究新型马氏体沉淀硬化不锈钢PH13-8Mo在含饱和H_2S的NaCl溶液中的腐蚀行为,利用极化曲线、电化学阻抗谱等电化学测试和浸泡实验相结合的方法,通过扫描电子显微镜(SEM)和X射线光电子能谱分析技术(XPS),观察了该高强钢在含H_2S的除氧和不除氧的NaCl溶液中的腐蚀形貌,并对其腐蚀产物的成分进行了分析.结果表明:在除氧的NaCl溶液中,阳极极化曲线的形状发生了明显的变化,电化学阻抗谱的容抗弧的幅值也较未除氧的溶液中变小;在除氧的NaCl溶液中浸泡7 d后,由于H_2S水解后的S~(2-)或HS~-离子侵入到钝化膜的内部,并与钝化膜或金属基体发生反应,使得试样表面发生全面腐蚀,腐蚀产物主要为Fe、Cr、Ni、Mo的氧化物和硫化物;而在未除氧的NaCl溶液中浸泡后,试样表面仅发生局部腐蚀.     

Development of solid state embeddable reference electrode for corrosion monitoring of steel in reinforced concrete structures

Corrosion of steel reinforcement concrete structures is monitored through the surface mounting techniques using liquid based reference electrodes. Due to the limited usage of liquid based reference electrodes solid state reference electrode are introduced recently. In the present study, we fabricated and characterized Mn₃O₄ based pellet electrode for corrosion assessment of steel rebar in high alkaline medium through electrochemical methods and the results are compared with conventional saturated calomel reference electrode (SCE). The results indicate that the fabricated pellet electrode exhibits better characteristics suitable for high alkaline concrete environment and differentiate the passive and active status of steel rebar.     

Effects of phosphate on the chloride-induced corrosion behavior of reinforcing steel in mortars

The influence of phosphate as a corrosion inhibitor on the corrosion behavior of as-received and pre-rusted reinforcing steels in mortar specimens was investigated after 360 days exposure in 3.5% NaCl solution. This involved the use of electrochemical techniques for studying the steel surface reactions and microscopic observations of the steel–mortar interface. The electrochemical methods, including electrochemical impedance spectroscopy (EIS) and measurements of corrosion potential (E_corr) and linear polarization resistance (LPR), were employed to evaluate the corrosion tendency and general corrosion rate of steel. In addition, the pitting corrosion resistance of steel was also determined by cyclic polarization (CP) measurements. The results indicate that different from nitrite, which is generally accepted as an anodic inhibitor, phosphate may be a cathodic inhibitor according to its reduced corrosion rate and more negative E_corr at the same dosage as nitrite in mortar specimens. The study also reveals that the inhibiting efficiency of phosphate against general corrosion of both as-received and pre-rusted specimens is lower than 10%, which is inferior to nitrite in some respects. However, as indicated by cyclic polarization measurements, the presence of phosphate provides slightly higher pitting corrosion resistance in comparison to nitrite. Furthermore, it suggests that the corrosion inhibition mechanism of phosphate in mortars mainly depends on a dual effect occurring at the steel–mortar interface. Furthermore, it is confirmed that phosphate has little effect on the long-term mechanical properties of mortars.     

复合缓蚀阻垢剂对模拟循环冷却水中Q235碳钢的缓蚀与阻垢性能

为寻找性能更优的缓蚀阻垢剂,采用静态失重、静态阻垢、电化学测试、X射线粉末衍射(XRD)、扫描电镜(SEM)等方法,研究了聚环氧琥珀酸(PESA)、羟基乙叉二膦酸(HEDP)及其复合物对模拟循环冷却水中Q235碳钢的缓蚀与阻垢性能。结果表明:复合缓蚀阻垢剂对Q235碳钢的缓蚀率和阻垢率均达到90%以上,其缓蚀、阻垢性能明显优于单组分PESA和HEDP;复合缓蚀阻垢剂是以抑制阴极反应为主的缓蚀剂,能很好地发挥各组分间的协同作用,在碳钢表面形成保护膜,抑制其在循环冷却水中发生腐蚀;复合缓蚀阻垢剂有助于Ca CO3垢样的分散和球霰石晶型的形成,起到较好的阻垢分散作用。     

Interactions between nitrites and Fe(II)-containing phases during corrosion of iron in concrete-simulating electrolytes

The influence of sodium nitrite on the corrosion processes of iron in solutions simulating polluted concrete was investigated by means of electrochemical methods, such us potentiodynamic, galvanostatic and impedance spectroscopy tests, coupled with analyses of the corrosion layers by Mössbauer spectroscopy. NO ₂ ^? ions are anodic inhibitors and provoked consequently an important increase of the corrosion potential. The polarisation curves show that NO ₂ ^? ions increase the pitting potential value. The size of electrochemical impedance spectra obtained at the OCP increases with the concentration of nitrite, which confirms the decrease of the corrosion rate. Galvanostatic experiments allowed us to provoke active corrosion even in presence of NO ₂ ^? . When nitrite ions are not present, the corrosion products mainly consist of iron (II) compounds, FeCO₃ or Fe(OH)₂ depending on the pH, and iron(II)–iron (III) compounds, i.e. green rusts (GRs). The main effect of nitrite ions was to accelerate the oxidation of GRs into FeOOH phases, confirming their oxidizing role. While immersed for long periods in the nitrite containing solutions, the α-iron foils do not present any single trace of corrosion.     

Efficiency of coatings applied on rebars in concrete

The performance of three reinforcing steel bars (rebars) coatings is analyzed by means of electrochemical methods. The coatings are representative of those commonly used during the repair of concrete structures affected by corrosion in the coastal regions of Argentina: an epoxy rust conversion coating, a zinc-rich epoxy, and a sprayed zinc coating. Two exposure conditions were investigated: immersed in a saline solution (wet) and exposed to an indoors atmosphere (dry). The rebar corrosion potential (E_corr), the corrosion rate (CR) and the electrical resistance (R) between bars were measured during approximately 800 days. In the dry condition the three coatings presented a satisfactory performance characterized by passive E_corr values and CR values lower than 1 m/year. On the other hand, the performance of the coatings in the wet condition depended on their formulations. The rust conversion coating showed active E_corr values and CR values higher than those measured on the uncoated bars. The zinc-rich epoxy and the sprayed zinc coatings presented E_corr values typical of active zinc. This indicates a certain degree of cathodic protection provided to the reinforcing steel. Besides, R values showed that in this condition, coatings do not provide a barrier type of protection.     

Evaluation of the Corrosion Protection Performance of Epoxy-Coated High Manganese Steel by SECM and EIS Techniques

The corrosion protection performances of epoxy-coated Mn steel and carbon steel were evaluated by electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SECM) analysis. EIS was performed on coated Mn steel with a scratch in a 0.1 M NaCl solution after a wet/dry cyclic corrosion test. The charge transfer resistance (R _ct) and film resistance (R _f) of the coated Mn steel displayed a higher value than the coated carbon steel. The increase in the charge transfer resistance and film resistance of the coated steel is due to the presence Mn in steel. SECM was conducted to estimate the corrosion protection performance of the epoxy-coated Mn steel immersed in a 0.1 M NaCl solution. It was found that dissolution of Fe²⁺ was suppressed at the scratch on the coated Mn steel due to the higher resistance for anodic dissolution of the substrate. SEM/EDX analysis showed that Mn was enriched in corrosion products at a scratched area of the coated steel after corrosion testing. FIB-TEM analysis confirmed the presence of the nanoscale oxide layer of Mn in the rust of the steel, which had a beneficial effect on the corrosion resistance of the coated steel by forming protective corrosion products in the wet/dry cyclic test.     

The shielding effect of wild type iron reducing bacterial flora on the corrosion of linepipe steel

Microbiologically influenced corrosion (MIC) by microbes capable of iron reduction (iron reducing bacteria (IRB)) on API 5L ×52 carbon steel coupons was investigated. A wild type of IRB was isolated and cultivated from a water sample collected from a sour oil well located in Louisiana, USA. 16S rRNA gene sequence analysis indicated that the mixed bacterial consortium contained two phylotypes close to members of the Proteobacteria (Shewanella oneidensis sp.) and Firmicutes (Brevibacillus sp.). The corrosion behavior of carbon steel coupons exposed to different media, with and without these microbes, was characterized by open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and polarization resistance (R_p), and a corrosion mechanism has been proposed. The biofilm and pit morphology that developed with time were characterized using field emission scanning electron microscopy (FESEM). Interestingly, surface morphology and electrochemical evaluations confirmed that IRB metabolic activities and resulting biofilms inhibit the corrosion process. The maximum corrosion rate in the biotic system was 4 mpy, while it was 20 mpy in the abiotic solution. Minor isolated pits were revealed in the biotic system, whereas extensive general pitting was found in the abiotic system. Elemental analysis and corrosion product structures were characterized by energy-dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). XRD confirmed the formation of a significant amount of iron oxide compounds that include iron, Hematite (Fe₂O₃), Magnetite (Fe₃O₄) and iron (II) hydroxide Fe(OH)₂ on the steel surface exposed to a biotic system.     

Protection of reinforcement steel corrosion by phenylphosphonic acid pre-treatment PART II: Tests in mortar medium

A pre-treatment of steel reinforcement in mortar by a 72 h immersion in 0.1 M phenyl-phosphonic acid (C₆H₅P(O)(OH)₂; PPA) was investigated. Then effectiveness of this procedure for protection against the corrosion of steel bars embedded in pre- or post-addition of sodium chloride mortar was evaluated by electrochemical impedance spectroscopy, visual inspection, SEM, and EDS analyses.The results showed that for non-treated steel reinforcement, the charge transfer resistance (R_t) decreases considerably with time indicating a very advanced state of corrosion after 54 months corrosion test. In contrast, for pre-treated steel rebar, this resistance remains high reflecting the effectiveness of the pre-treatment method against corrosion. The corrosion rate evaluated from the charge transfer resistance at 54 months corrosion in chloride containing medium was 0.5 μm year⁻¹.     

Effect of four coating structures on corrosion kinetic of galvanized reinforcement in concrete

In the present work is described the effect of the characteristics of the galvanized coating on corrosion rate of reinforcing bars embedded in a concrete without additives and in another with 2% CaCl₂ in terms of cement weight. To this end, the following materials were subjected to the action of a moisture saturated atmosphere for a period of400 days: an annealed-galvanized coating; another one obtained by dipping in a molten Zn bath with0.025% Al and some others produced at450 and430°C in an ordinary bath. The attack evolution vs time was controlled by measuring the polarization resistance. The electrochemical determinations were gravimetrically verified and supplemented by a metallographic examination of tests coatings. In the absence of chlorides, the attack is fully tolerated. Chlorides radically change the corrosion behaviour of galvanized steel and increase the attack by a factor of2.8 in the most favourable case, but in these conditions, coatings with thick, homogeneous η layer outperform the usual ones, and specially the annealed ones.     

Corrosion and impedance studies on magnesium alloy in oxalate solution

Corrosion behavior of AZ91E alloy was investigated in oxalate solution using potentiodynamic polarization and electrochemical impedance measurements (EIS). The effect of oxalate concentration was studied, where the corrosion rate increases with increasing oxalate concentration. The effect of added ions (Br⁻, Cl⁻ or SiO₃²⁻) on the electrochemical behavior of magnesium alloy in 0.1 M Na₂C₂O₄ solution at 298 K, was investigated. It was found that the corrosion rate of 0.1 M oxalate solution containing silicate ion is lower than the blank (0.1 M Na₂C₂O₄). This was confirmed by scanning electron microscope (SEM) observations. However, for the other added ions Br⁻ or Cl⁻, the corrosion rate is higher than the blank.