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.     

Mitigation of chloride driven stress corrosion cracking susceptibility of 316L austenitic stainless steel using plasma sprayed TiO2 coating

The present study proposes a protective TiO₂ coating against chloride driven stress corrosion cracking problem of 316L austenitic stainless steel. To test the performance of the proposed coating, the severe chloride-based boiling magnesium chloride solution at 155 °C was chosen. For experimentation, the constant strain-based U-bend specimens were coated with TiO₂ using atmospheric plasma spray method. The results indicated higher resistance by TiO₂ coated specimens against stress corrosion cracking problem, while the bare specimens experienced severe damage in the boiling magnesium chloride solution under various strain loading configurations. The coating-electrolyte system of TiO₂ coated sample demonstrated over seven times higher resistance, eventually led to reduction in corrosion rate over fifteen times compared to the bare 316L stainless steel in the boiling magnesium chloride solution. This improved performance of the coated 316L stainless steel is attributed to inhibition of outward diffusion of iron-chromium-nickel in the corrosive environment and the high chemical stability of TiO₂.     

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.     

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.     

Microstructural investigations of Ni and Ni2Al3 coatings exposed in biomass power plants

Abstract

The present work investigates the corrosion resistance of Ni and Ni₂Al₃ coated austenitic stainless steel (TP347H) tubes, which were exposed in a biomass-fired boiler with an outlet steam temperature of 540 °C for 6757 h. The Ni₂Al₃ coating was produced by electroplating Ni followed by low temperature pack cementation. After exposure, microstructural investigations were performed by light optical and electron microscopy (SEM-EDS). Electroplated Ni coatings were not protective in straw firing power plants and exhibited similar corrosion morphology as uncoated tubes. For Ni₂Al₃ coatings, the nickel aluminide layer was no longer adherent to the tube and was only found within the deposit. However, Ni₂Al₃ coatings had provided some protection compared to uncoated and Ni coated tubes. The formation of nickel chloride binds aggressive chlorine and slows down the active oxidation mechanism. In local areas, sulphidation corrosion attack of Ni was detected.     

Impact of mechanical loading on the corrosion of steel reinforcement in concrete structures

This paper presents results of an experimental investigation on the effect of mechanical loading on the corrosion of steel reinforcement in concrete. Reinforced concrete beams were cast, subjected to mechanical loadings and then exposed to corrosive environment. Successive drying and wetting cycles using 3% sodium chloride salt solution were used to accelerate the corrosion attack. Electrochemical techniques such as macrocell corrosion current, linear polarization resistance (LPR), corrosion potential (E _corr ) and electrochemical impedance spectroscopic (EIS), were used to evaluate the corrosion behavior of the reinforcement. Also, chloride penetration profile and visual inspection of the beam rebars were obtained. The results shows that the pre-exposure mechanical load has no influence on the corrosion initiation or corrosion rate thereafter, unless it reaches to some limit where it develops connected cracks through which the chloride ions flow and depassivate the rebars. The load of 25% of the ultimate capacity seems to be the critical load limit where some microcracks onset to be connected, facilitate the chloride ions flow, and initiate the rebar corrosion.     

Improve corrosion resistance of magnesium in simulated body fluid by dicalcium phosphate dihydrate coating

A dicalcium phosphate dihydrate (DCPD) coating composed of bar-shaped crystals was deposited on the surface of magnesium in order to slow down the corrosion rate of the substrate. The corrosion resistance of the DCPD-coated specimens was evaluated in a simulated body fluid (SBF) with uncoated specimens as a control. Time-dependent characteristics of specimens and the corresponding SBF were analyzed at 3, 5, 7, 14 and 21 days of immersion. Less weight loss and pH increase were observed for the coated group than the uncoated group. The coating was intact after 3 days of immersion although its dissolution was manifested by XRD examination. Noticeable DCPD dissolution occurred at the 5th day accompanied by a temporary increase in Ca and P concentrations in SBF which otherwise kept decreasing. Despite the dissolution of the coating, some DCPD particles were still observed on the surface of the substrate after 21 days of immersion. In contrast to the coated specimens, a porous layer of Mg(OH)₂ was formed on the surface of uncoated specimens at the 5th day of immersion. It was found that the corrosion rate of the coated group was substantially lower than that of the control.     

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.     

Corrosion behaviour of rebars in fly ash mortar exposed to carbon dioxide and chlorides

Addition of fly ash has beneficial effects on some mechanical properties of concrete, as well as on the corrosion process induced by the chloride ion. The aim of this study was to investigate the effect of fly ash addition on the corrosion process occurring in reinforced concrete exposed simultaneously to carbon dioxide and chloride. The corrosion process of steel rebars embedded in mortar with 15% and 30% of fly ash was tested under carbon dioxide and sodium chloride contamination. Monitoring of open circuit potential and electrochemical impedance spectroscopy (EIS) were used to follow the corrosion process. Results have shown that under accelerated carbonation fly ash mortar shows higher corrosion rates. The chloride content in mortar exposed to accelerated carbonation increases with the amount of fly ash. However, under natural carbonation it decreases with the addition of fly ash.     

A short-term test method to determine the chloride threshold of steel–cementitious systems with corrosion inhibiting admixtures

Now-a-days, multiple types of corrosion inhibiting admixtures (CIAs) are being used to enhance the chloride threshold (Cl_th) of steel–cementitious systems. However, due to the application of external potential to drive chlorides, some existing short-term test methods are not suitable to assess the Cl_th of S–C systems with CIAs containing anions. This paper presents the development of a Modified Accelerated Chloride Threshold (mACT) test to determine the Cl_th for S–C systems with CIAs. The test specimens consisted of a mortar cylinder with an embedded steel piece and electrodes forming a 3-electrode corrosion cell. The specimens were exposed to chloride solution and the linear polarization resistance tests were conducted every 3.5 days. The corrosion initiation was detected using statistical analysis of the repeated R _p measurements. After corrosion initiation, the chloride content in mortar adjacent to the embedded steel piece was determined and defined as Cl_th. The time required to complete mACT test for an S–C system with CIAs is about 120 days. The Cl_th of eight specimens each with S–C system containing (i) without inhibitor, (ii) anodic inhibitor [calcium nitrite] and (iii) bipolar inhibitor [both calcium nitrite and amino alcohol] were determined. Both anodic and bipolar CIAs showed enhanced corrosion resistance. Also, the bipolar inhibitor performed better than anodic inhibitor. It was concluded that the use of CIAs could significantly delay the initiation of chloride-induced corrosion. The mACT test can be used to determine the Cl_th and estimate the service life during the planning and design stages of a project and help select durable materials.     

Corrosion behaviour of steel in high alumina cement mortar cured at 5,25 and 55 °C: chemical and physical factors

The corrosion behaviour of embedded steel was related to the composition of the pore phase in equilibrium with the hydrated phases and the porosity of the high alumina cement mortars subsequent to curing at 5,25 and 55 °C. The corrosion of reinforcements was evaluated by electrochemical techniques. The effect on corrosion of 3% by weight of cement of NaCl, added during the mixing process, and of the accelerated carbonation of mortars in CO₂ atmosphere were also determined. The pH value and the chemical composition of pore fluid of plain high alumina cement (HAC) mortar cured at all three temperatures suggested that the embedded steel was in a passivated state. The resistance of HAC to carbonation and its greater potential for chloride binding by chloroaluminate formation are believed to make HAC inherently more protective to steel, relative to normal Portland cement, during ingress of chloride from external sources. High corrosion rates reported in literature for steel embedded in HAC may be attributable to bad practice, not to lack of passivity.     

Influence of coating on short steel fiber reinforcements on corrosion behavior of aluminium base short steel fiber reinforced composites

Steel fiber reinforced aluminium composites are attractive materials of high specific strength but exhibit poor resistance against electrochemical corrosion. The study discusses the electrochemical corrosion behavior of uncoated, copper and nickel coated short steel fiber reinforced aluminium and Al–2Mg matrix composites in 1 (N) NaCl solution. Galvanic corrosion between the steel fiber and aluminium governs the corrosion behavior of these composites. It has been observed that open circuit potential (OCP) is shifted to more negative side with copper coating on the fibers and to the more positive side on coating the fibers with nickel. Compared to the uncoated fiber higher corrosion current density indicates corrosion rate was observed for the copper coated fiber reinforced composites where as a lower current density was noted for the nickel coated fiber reinforced composites was observed. Addition of 2 wt% magnesium to aluminium alloy matrix increased the corrosion current density. The corrosion mechanism in these composites is dominated by galvanic cell formation that is evident from the dissolution of Al matrix near the peripheral region of steel fibers.     

Electrochemical behaviour of chromium nitride coatings with various preferred orientations deposited on steel by unbalanced magnetron sputtering

Abstract

Chromium nitride coatings Cr₂N(111) and preferred orientations of CrN(111) and CrN(200) were successfully deposited on AISI 304 stainless steel by an unbalanced magnetron sputtering method. The electrochemical corrosion properties of the deposited films were studied in a 0·5M H₂SO₄ + 1M NaCl aqueous solution at ambient temperature by electrochemical measurements, including the corrosion potential E _corr, linear polarisation, potentiodynamic polarisation and electrochemical impedance spectroscopy. The structural characterisation and surface morphology were investigated using X-ray diffraction, scanning electron microscopy and atomic force microscopy. The experimental results indicated that the CrN(200) coating possesses the best corrosion resistance property, followed by the CrN(111) coating, while the Cr₂N coating has the least resistance among the three types of CrN(111), CrN(200) and Cr₂N(111) coatings. The porosity, corresponding to the ratio of the polarisation resistance of the uncoated and the coated substrates, was higher in the Cr₂N(111) coating than in the other CrN coatings. The CrN(200) coating had a dense microstructure almost without porosity. The void defects of CrN(111) and Cr₂N(111) coatings are responsible for the decrease in corrosion protection.     

Corrosion behaviour and bioactivity of electrophoretically deposited hydroxyapatite on titanium in physiological media (Hanks’ solution)

Hydroxyapatite (HA) coatings were developed on titanium by electrophoretic deposition at various deposition potentials from 30 to 60 V and at a constant deposition time of 5 minutes using the synthetic HA (Ca₁₀(PO₄)₆(OH)₂,) powder in a suspension of dimethyleformamide (DMF, HCON(CH₃)₂). The electrochemical corrosion behavior of the HA coatings in simulated body fluid (SBF Hanks?? solution) at 37 °C and pH 7.4 was investigated by means of open-circuit potential (OCP) measurement and potentiodynamic polarization tests. The OCP test showed that the values OCP for the coated samples shifted to more noble potential than for uncoated titanium, especially after addition of dispersants. The polarization test revealed that all HA coated specimens had a corrosion resistance higher than that of the substrate, especially after addition of dispersants such as polyvinyl butyral (PVB), polyethylene glycol (PEG) and triethanolamine (TEA) to the suspension. The coating morphology after polarization, characterized by scanning electron microscopy (SEM), showed penetration of electrolyte into the HA coats. Bone bioactivity of the coatings was also studied by immersion of coated specimens in Hanks?? solution for 3 and 7 days. Apatite granules growth on the surface of the HA layers was observed.     

Nanoindentation and SEM/EDX characterization of the geopolymer-to-steel interfacial transition zone for a reactive porcelain enamel coating

The increasing use of alternative cementitious materials such as geopolymers as an environmentally-friendly alternative to traditional cements requires an improved understanding of the interfacial transition zone (ITZ) between the matrix and reinforcing steels. In this study, nanoindentation measurements were spatially coupled to images with scanning electron microscopy and chemical composition using energy dispersive X-ray microanalysis. The study focused on the microstructure and chemical composition of the interfacial transition zone (ITZ) for reinforcing steel embedded in a geopolymer mortar. The ITZ was analyzed for uncoated steel and steel coated with a reactive porcelain enamel that improves bonding and corrosion resistance. Results indicate that a more gradual transition of mechanical properties and chemical composition for the coated steel coupled with improved integration to the mortar correlates to increased bond strength measured in macroscale experiments.     

Deformation capability and protective role of zirconia coatings on stainless steel

ZrO₂ coatings were obtained by the alkoxide route and deposited on to stainless steel using the dip-coating technique. The starting solutions were prepared by mixing zirconium tetrabutoxide, isopropanol, acetylacetone. The water content for the hydrolytic reaction came from atmospheric moisture. These coatings were characterized by scanning electron microscopy, X-ray fluorescence, Fourier transform-infrared spectroscopy, and X-ray diffraction. Their deformation capability was studied by using the stretch deformation test. It is worth noting that these coatings deposited on stainless steel have the capacity to deform extensively without apparent cracks or fracture. Their ability to protect the metallic substrate against corrosion, in a neutral chloride medium, was investigated. For this purpose, the pitting potential of the coated metal was measured by the potentiodynamic polarization technique and the a.c. impedance diagram of the coating was recorded in the potentiostatic mode at the rest potential. The variation in the pitting potentials revealed a temporary increase in the corrosion resistance of coated stainless steel, which disappeared after ageing of the coatings in the chloride solution. During ageing, the coating resistance deduced from the complex diagram via an equivalent circuit, decreases, thus showing a deterioration.     

Electrochemical study of corrosion inhibition of steel reinforcement in alkaline solutions containing phosphates based components

The aim of this study is to investigate the viability of use of sodium phosphate (Na₃PO₄: SP), tetrasodium pyrophosphate (Na₄P₂O₇: TSPP) and hydroxyethylidene-diphosphonic acid (C₂H₈O₇P₂: HEDP) as a non-toxic corrosion inhibitors of steel bars in alkaline media which simulate the electrolyte in the concrete pores. The effectiveness of these phosphate compounds as corrosion inhibitors was investigated by measuring the corrosion potentials, the polarization curves, the corrosion current densities, and the electrochemical impedance spectroscopy of steel bars immersed for 30 days in saturated Ca(OH)₂ solutions with and without chlorides. At the completion of the tests, the mass losses were determined in order to verify the reliability of the electrochemical results. The results showed that phosphate compounds form a protective layer on the steel surface when immersed in alkaline solution without chlorides. In the presence of chloride ions, the SP acts as an anodic inhibitor and reduces the corrosion activity on steel. The HEDP shows lower efficiency, probably due to the decrease of the pH and to the high [Cl⁻]/[inh] ratio used. Results obtained by electrochemical and gravimetric methods are in quite reasonable agreement.     

Corrosion behavior of plasma sprayed ceramic and metallic coatings on carbon steel in simulated seawater

Al₂O₃, ZrO₂ and Ni60 coatings were produced on carbon steels by plasma spray. Ni60 was used as the bond coat in all the cases. The microstructure of these coatings was analyzed by scanning electron microscopy (SEM). The corrosion behavior of the plasma spray coated samples as well as uncoated samples was evaluated by open circuit potential (OCP) measurements, potentiodynamic polarization tests, and electrochemical impedance spectroscopy (EIS) in simulated seawater. The results showed that Ni60 coating protected carbon steels against the corrosion and plasma spraying ceramic powders on metallic coating improved the corrosion resistance of the coatings further. The corrosion resistance of the Al₂O₃ coating was superior to that of the ZrO₂ coating due to the relatively few defects in Al₂O₃ coating.     

Steel protection capacity of polymeric based cement mortars against chloride and carbonation attacks studied using electrochemical polarization resistance

This work analyzes the protection capacity of modified Portland cement mortar with polymers: styrene butadiene, acrylic latex with reinforced plastic fibres and acrylic latex with silica fume, using the electrochemical polarization resistance (R_p) technique to monitor the behaviour of steel bars embedded in the specimens, when placed in environments with CO₂ and chloride. Results indicate that only chemical, physical and mechanical characterizations are not sufficient to classify these materials from the point of view of protection against aggressive agents. There is evidence that material performance depends on workability, chemical composition of squeezed pore solution in addition to the porosity and resistivity which have an important role in the protection against the corrosion of steel bars.     

Characterization and corrosion behavior of electroless Ni–P/nano-SiC coating inside the CO2 containing media in the presence of acetic acid

In this research, Ni–P and Ni–P/nano-SiC coatings were applied on the X70 steel substrate successfully without any surfactant. Then, CO₂ corrosion in the presence of acetic acid (HAc) was investigated using electrochemical techniques. Scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) techniques were used for surface analyses of the coatings. The electrochemical behavior of corrosion was investigated using polarization test and electrochemical impedance spectroscopy (EIS). XRD pattern of Ni–P/nano-SiC coating was very similar to that of Ni–P coating. EDS results demonstrated the presence of SiC particles in the coating. SEM images confirmed the presence of SiC nano-particles with almost uniform distribution in the coating. The corrosion current density was less in the Ni–P and Ni–P/nano-SiC coated samples than uncoated X70 steel. Ni–P/nano-SiC coated sample had the most corrosion resistance because of less effective metallic area available for corrosive media. The overall protection mechanism of Ni–P and Ni–P/nano-SiC coatings was achieved by formation of a layer of adsorbed hypophosphite anions (H₂PO₂⁻).