Electrochemical injection of organic corrosion inhibitors into carbonated cementitious materials: Part 1. Effects on pore solution chemistry

This series of investigations was intended to clarify phenomena associated with electrochemical injection of the organic base corrosion inhibitors, ethanolamine and guanidine, into carbonated concrete. In Part 1, experiments were conducted with laminated specimens of carbonated cement paste, that were specially designed to facilitate analysis with adequate spatial resolution to assess changes in their pore solution phase chemistry after they had been subjected to constant current electrolysis between embedded cathodes and external anodes. The anolyte solutions provided sources of ethanolamine or guanidine in contact with the exterior specimen surfaces. Effects of variations in the applied current density and duration of electrolysis on the concentration profiles of the two inhibitors and the other main constituents of the pore solution phase were determined. The results have been used to underpin the development of a mathematical model, which is described in Part 2.     

Corrosion inhibitor systems for remedial treatment of reinforced concrete. Part 2: sodium monofluorophosphate

Sodium monofluorophosphate (MFP) has been applied in the form of concentrated aqueous solutions to the surfaces of concrete structures with the aim of inhibiting corrosion of embedded reinforcing steel which has become depassivated as a consequence of carbonation and/or chloride contamination. To evaluate the effectiveness of such treatments, a series of laboratory investigations was undertaken with reinforced concrete specimens that were chloride-contaminated to varying extents in the presence or absence of carbonation. The corrosion responses of embedded steel bars at various depths of cover were monitored electrochemically during a controlled programme of cyclic wetting and drying undertaken for several months prior to the inhibitor treatment and for approximately 18 months thereafter. Gravimetric measurements of the quantities and distribution of corrosion on the steel were also made on completion of the exposure tests. It has been found that there were no marked reductions in the corrosion rates of the steel under the conditions investigated. Analysis of aqueous extracts from the treated concrete specimens by means of ion chromatography revealed that negligible penetration of soluble MFP ions had occurred into any of the specimens. Hydrolysis products of MFP (phosphate and fluoride) were present at significant depths in aqueous extracts of the carbonated concrete specimens but only fluoride was detectable in similarly obtained aqueous extracts of non-carbonated specimens.     

Investigations of an ethanolamine‐based corrosion inhibitor system for surface treatment of reinforced concrete

Laboratory investigations were performed to assess the efficacy of a proprietary ethanolamine‐based corrosion inhibitor system when applied to the surface of reinforced concrete specimens that were chloride‐contaminated to varying extents in the presence or absence of carbonation. The corrosion responses of embedded steel bars at various depths of cover were monitored electrochemically during a controlled programme of cyclic wetting and drying undertaken for several months prior to the inhibitor treatment and for approximately eighteen months thereafter. Gravimetric measurements of the quantities and distribution of corrosion on the steel were also made on completion of the exposure tests. Analysis of aqueous extracts from treated concrete revealed that the ethanolamine component of the inhibitor system penetrated to depths of more than 15 mm within the concrete. It was found that, for inhibitor‐treated specimens, there was some reduction in the corrosion rate of pre‐corroding steel at low cover depths in non‐carbonated concrete with modest levels of chloride contamination. At higher levels of chloride contamination and in carbonated specimens, however, the ethanolamine‐based inhibitor was apparently ineffective under the conditions investigated.     

Corrosion inhibitor systems for remedial treatment of reinforced concrete. Part 1: calcium nitrite

Laboratory investigations were performed to assess the efficacy of calcium nitrite as an inhibitor when used in surface treatments applied to reinforced concrete specimens that were chloride contaminated to varying extents in the presence or absence of carbonation. The corrosion responses of embedded steel bars at various depths of cover were monitored electrochemically during a controlled programme of cyclic wetting and drying undertaken for several months prior to the inhibitor treatment and for approximately 18 months thereafter. On completion of the exposure tests, measurements of corrosion weight losses and their distribution on the steel surfaces were also made. In non-carbonated specimens with high levels of internal chloride and carbonated specimens with even low levels of internal chloride, the surface-applied inhibitor treatment appeared to be ineffective under the conditions of the experiments and enhancement of local corrosion rates was observed in some specimens.     

Corrosion of Carbon Steel and Corrosion-Resistant Rebars in Concrete Structures Under Chloride Ion Attack

Corrosion of reinforced concrete is the most challenging durability problem that threatens reinforced concrete structures, especially structures that are subject to severe environmental conditions (i.e., highway bridges, marine structures, etc.). Corrosion of reinforcing steel leads to cracking and spalling of the concrete cover and billions of dollars are spent every year on repairing such damaged structures. New types of reinforcements have been developed to avoid these high-cost repairs. Thus, it is important to study the corrosion behavior of these new types of reinforcements and compare them to the traditional carbon steel reinforcements. This study aimed at characterizing the corrosion behavior of three competing reinforcing steels; conventional carbon steel, micro-composite steel (MMFX-2) and 316LN stainless steel, through experiments in carbonated and non-carbonated concrete exposed to chloride-laden environments. Synthetic pore water solutions have been used to simulate both cases of sound and carbonated concrete under chloride ions attack. A three-electrode corrosion cell is used for determining the corrosion characteristics and rates. Multiple electrochemical techniques were applied using a Gamry PC4? potentiostat manufactured by Gamry Instruments (Warminster, PA). DC corrosion measurements were applied on samples subjected to fixed chloride concentration in the solution.     

Electrochemical injection of organic corrosion inhibitors into carbonated cementitious materials: Part 2. Mathematical modelling

A mathematical model is presented for simulation of changes in the pore solution phase chemistry of carbonated hardened cement paste when aqueous solutions of organic base corrosion inhibitors are applied to the surface of the material and constant current densities in the range of 1-5 A/m² are passed between anodes placed within the inhibitor solutions and steel mesh cathodes embedded within the paste. The model, based on the Nernst-Planck equation, is used to predict the concentration profiles of electrochemically injected inhibitors and the major ionic species present within the pore electrolyte. For two specific organic base inhibitors with widely different pK_a values, viz. ethanolamine (pK_a 9.5) and guanidine (pK_a 13.6), the model predictions are compared with experimental results described in Part 1 of the investigations.     

Effect of humidity and chloride content on the corrosion of steel embedded in LWA concrete

Measurements have been made with mortar specimens with light aggregates (LWA) and the cements Norcem HS65 and MP30, corresponding to CEM I and CEM II. The w/b ratio was 0.30 and 0.40 and in one mix prewetted LWA was used. The silica fume addition was 8%. The specimens have two sets of electrodes consisting of a 10 mm reinforcing steel and a 10 mm rod of stainless steel. In the start of the experiment the chloride penetration was accelerated by applying a voltage between a negatively charged steel plate within the salt solution and a positively charged net of stainless steel embedded in the concrete above the reinforcing steels. This caused some problems and the set-up was changed to using a Plexiglas brim and a solution of calcium hydroxide and sodium chloride was applied. In the solution, a titanium net was placed and a positive voltage of 12 V was applied between the embedded steels and the net with the titanium net as the positive pole. Measuring galvanic currents, electrochemical potential and polarisation resistances have presented a good picture of the corrosion activity of the embedded steels. There is a distinct effect of the humidity upon the corrosion activity registered by the electrochemical measurements. There is a good relation between the electrochemical measurements and the observed corrosion attacks at the end of the experiments. The LWA concrete with water saturated aggregates showed more corrosion than the corresponding LWA concrete with dry aggregates. The rates of corrosion measured both as a galvanic current and as a function of the polarisation resistance showed that the concrete with watered aggregate concrete had a corrosion rate about twice as high as the corresponding LWA concrete with dry aggregates. There are marked differences in the chloride penetration for the different cements. Effects have been observed on the chloride content of the different concretes. Lower w/b ratio, MP30 cement compared to HS65 and no prewatering of the LWA gave less chloride penetration.     

Corrosion inhibitors in reinforced concrete structures Part 3 – migration of inhibitors into concrete

Abstract

To prevent and control rebar corrosion in concrete, corrosion inhibitors may be used both as a preventative technique if added to fresh concrete and as a repair system if applied to hardened concrete. In the past six years, an experimental research was performed on both mixed and migrating inhibitors. Effectiveness of mixed inhibitors has been investigated in Part 1: the ability to delay time to corrosion and to reduce corrosion rate has been studied both in the case of chloride-induced corrosion and carbonated concrete. Organic migrating inhibitors were applied to concrete specimens, and their ability to control corrosion was investigated: results are described in Part 2. Results allow to state that the inhibitors are able to delay time to corrosion, while a negligible effect was observed in the reduction of corrosion rate. In the third part, the inhibitor migration into concrete has been analysed in order to quantify inhibitor penetration depth and main penetration mechanism.     

Corrosion behaviour of corrugated lean duplex stainless steels in simulated concrete pore solutions

This work studies the corrosion behaviour of two corrugated lean duplex stainless steels (SAF 2001 and 2304 grades) in eight alkaline solutions (carbonated and non-carbonated, saturated Ca(OH)₂ solutions with different chloride contents). 2001 stainless steel is a new grade in market because of its composition. 2304 is a grade previously studied under different conditions. However, its use as reinforcement in concrete is new. Studies are carried out by polarization curves following scanning electronic microscopy (SEM) and optical observations. Results are compared to those of carbon steel and austenitic AISI 304 and duplex SAF 2205 under similar conditions. After corrosion tests in alkaline media with chloride, ferrite tends to corrode selectively in 2304 duplex, while austenite corrodes selectively in 2001 under the same conditions. The influence of the duplex microstructure on attack development and morphology is analyzed. The electrochemical parameters obtained from the polarization curves suggest 2001 could replace 304 keeping the structure its corrosion performance (and with clear economical advantages). 2304 shows better corrosion behaviour than the more expensive 304, but somewhat lower than the excellent behaviour shown by 2205.     

Electrochemical realkalisation for rehabilitation of reinforced concrete structures

In steel reinforced and prestressed concrete structures depassivation of the reinforcing steel can take place due to carbonation of the concrete cover. Depending on humidity and oxygen availability subsequent corrosion reactions will be initiated. Such conditions require measures to exclude corrosion induced damages during the designed lifetime of the structure. In the last few years an electrochemical realkalisation treatment has been proposed as adequate rehabilitation technique for carbonated concrete. This temporary treatment should increase the pH-value of the concrete pore water solution due to penetration of alkaline electrolyte from the concrete surface as well as repassivate the reinforcement due to electro chemical reactions at the steel surface. In order to clarify the different mechanisms taking place during electrochemical realkalisation laboratory tests have been carried out using carbonated reinforced mortar specimens. The investigations were aimed at checking the influence of various parameters, e.g. treatment time and current density, as well as the efficiency and long-term durability of this rehabilitation method.     

Cover Picture: Materials and Corrosion. 9/2020

Cover: Corrosion behaviour of carbon steel was evaluated in pore solutions extracted from mortars made of diff erent blended cements. Pictured are corrosion products produced in the following conditions, from left to right, top to bottom: carbonated CEM II mortar with chlorides, non-carbonated CEM II mortar with chlorides, carbonated CEM III mortar with chlorides and noncarbonated CEM III mortar with chlorides. More detailed information can be found in: Miha Hren, Tadeja Kosec, Andraž Legat, Corrosion behavior of steel in pore solutions extracted from diff erent blended cements, Materials and Corrosion 2020 , 71, 759.     

Einflußeiner Verzinkung auf die Korrosion von mit Zementmörtel beschichtetem Stahl in NaCl-Lösung

Effect of galvanizing on the corrosion of steel in concrete immersed in NaCl solution Galvanized or pickled steel sheet specimens were embedded in portland cement mortar of various water cement ratios and curing conditions and then wholly or partially immersed in 0.5 M NaCl solution for 1 to 5 yrs. Free corrosion potentials and electrical resistances have been measured. Immersion conditions and the presence of zinc have a significant effect on the corrosion resistance of the embedded steel sheets. The potentials of the wholly immersed specimens are very negative. Thus, these specimens cannot act as cathodes in corrosion cells, and the steel sheets within the mortar do not corrode. The partially immersed specimens, on the other hand, show very noble potentials. Also in the case of galvanized steel sheets the potentials are shifted to the same positive values in the course of exposure time. Thus, all these specimens can act as cathodes in corrosion cells. Localized corrosion generally occurs at the water/air line. In the case of pickled specimens the mortar is cracked due to growing corrosion products. In the case of galvanized steels the corrosion is retarded significantly. The test results are discussed in detail with respect to practical problems of cell formation, internal and external protection of pipes as well as the corrosion resistance of reinforced concrete.     

Analysis of corrosion resistance behavior of inhibitors in concrete using electrochemical techniques

Reinforced concrete is one of the most durable and cost effective construction materials. However, in high chloride environments, it can suffer from corrosion due to chloride induced breakdown of the normal passive layer protecting the reinforcing steel bars inside concrete. One means of protecting embedded steel reinforcement from chloride induced corrosion is the addition of corrosion inhibiting admixtures. In the present investigation, various inhibitors such as sodium nitrite, zinc oxide, mono ethanol amine, diethanolamine, and triethanol amine have been used in concrete in different percentages. Their effectiveness was then studied using various electrochemical techniques such as rapid chloride ion penetration test, open circuit potential measurement, electrochemical impedance measurement, potentiodynamic polarization measurement, and gravimetric weight loss measurement. The results thus obtained indicate that the addition of inhibitors enhances the corrosion resistance properties.     

Influence of steel-concrete interface condition on galvanic corrosion currents in carbonated concrete

This paper presents specific experiments which were developed in order to assess galvanic currents in macrocell corrosion specimens involving active steel in carbonated concrete and passive steel in sound concrete. The influence of the steel-concrete interface condition on the galvanic current was also experimentally investigated. To focus on macrocell corrosion rate assessment, the initiation time of the corrosion process (concrete carbonation) was accelerated. FEM simulations were carried out in order to enhance the physical comprehension of these corrosion experiments. It was found that, in realistic condition, the electrical coupling of active and passive steel areas leads to high galvanic currents and consequently high corrosion levels according to RILEM recommendation. Moreover, steel-concrete interfacial defaults significantly increase the macrocell driving potential and, therefore, the galvanic corrosion current.     

Electrochemical corrosion parameters for active and passive reinforcing steel in carbonated and sound concrete

The electrochemical corrosion parameters, such as corrosion potential, corrosion current density, and the Tafel constants are necessary inputs for the corrosion modeling in reinforced concrete. Literature shows large variability in their values, whereas the data are scarce for the carbonated concrete. This paper presents a range of corrosion parameters for the active steel in carbonated and the passive steel in noncarbonated concrete. Forty-eight singly reinforced concrete cylinders were cast, of which 24 were carbonated and the others were sound samples. Potentiodynamic polarization curves were obtained at three different scan rates and extrapolated to extract the corrosion parameters. To validate these parameters, a macrocell corrosion system was simulated using FEM-based Comsol multiphysics® software. The numerical results were compared to two experimental studies. A natural dispersion in the values of corrosion parameters for both active and passive steels was observed. The average Stern–Geary constant was 54 and 47 mV for active and passive steels, respectively. Numerical simulations with the obtained parameters predicted the macrocell corrosion in partially carbonated concrete with a high accuracy. The presented values of corrosion parameters in this study could help researchers and engineers to simulate the corrosion phenomena in concrete accurately.     

Chloride threshold for rebar corrosion in concrete with addition of silica fume

The effect of silica fume on the chloride threshold for the initiation of pitting corrosion of steel in concrete was investigated. Laboratory tests were carried out in concrete specimens made with ordinary Portland cement and with 10% of silica fume. Chloride contents up to 2% by mass of cement were added to the mixes, in order to investigate the corrosion rate of embedded bars made of both strengthened and mild steel. A lower chloride threshold was observed in the bars which were embedded in concrete with silica fume compared to those embedded in concrete made of Portland cement.     

Repassivation of steel in carbonated concrete induced by cathodic protection

The paper discusses the peculiarities of cathodic protection applied to steel in carbonated concrete, which are strictly connected to the production of alkalinity at the steel surface. Results of a research on the application of cathodic protection to specimens with steel bars in carbonated concrete are discussed. A thin layer of concrete was realkalized within a period of 4–5 months by applying a current density of 10 mA/m² and steel could repassivate even in the presence of small contents of chlorides. A lower current density of 5 mA/m² could only maintain steel passive when the concrete in the vicinity of the steel had been previously realkalized through the application of a start‐up current density of 70 mA/m² for one month. Protection mechanisms are investigated and design of cathodic protection of steel in carbonated concrete is outlined. The possibility of obtaining protection on deeper rebars is also considered.     

Steel corrosion in concrete: Determinist modeling of cathodic reaction as a function of water saturation degree

The prediction of the long-term behavior of reinforced concrete structures involved in the nuclear waste storage requires the assessment and the modeling of the corrosion processes of steel reinforcement. This paper deals with the modeling of the cathodic reaction that is one of the main mechanisms of steel rebar corrosion. This model takes into account oxygen reduction and oxygen diffusion through a diffusion barrier (iron oxide and/or carbonated concrete) as a function of water saturation degree. It is demonstrated that corrosion rate of reinforcement embedded in concrete with water saturation degree as low as 0.9 could be under oxygen diffusion control. Thus, transport properties of concrete (aqueous and gaseous phase, dissolved species) are key parameters that must be taken into account to model electrochemical processes on the reinforcement.     

Effect of carbonation process on the passivating products of zinc in Ca(OH)2 saturated solution

The effect of carbonation process on the passivating layer of zinc in Ca(OH)₂ saturated solution was studied. The investigation was performed by means of corrosion potential, corrosion current density, and impedance measurements. To analyze the changes in the passivating layer, X‐ray diffraction, Raman spectroscopy and scanning electron microscopy (SEM) were utilized. The results obtained indicate that the layer of calcium hydroxyzincate (Ca[Zn(OH)₃]₂ · 2H₂O) (CHZ), which determines the passivity state of zinc both in Ca(OH)₂ saturated solution and in concrete, is destroyed by the carbonation process, in agreement with previous results obtained for galvanized steel embedded in concrete. X‐ray diffractometry and Raman spectroscopy showed that CHZ reaction with CO₂ leads to the formation of Zn₅(CO₃)₂(OH)₆ (hydrozincite) and CaCO₃ (calcite). SEM observation confirms the deep transformation in the passivating layer caused by carbonation. Corrosion potential and corrosion current density measurements show that zinc maintains its passive state also after carbonation. However, impedance measurements indicate that hydrozincite has lower passivating properties than calcium hydroxyzincate in the carbonated solution.     

Rebar corrosion in carbonated concrete exposed to variable humidity conditions. Interpretation of Tuutti’s curve

This paper deals with the modelling of the rebar corrosion kinetics in unsaturated concrete cover. The concrete is assumed carbonated resulting in an active corrosion of steel. The corrosion kinetics is coupled with the ionic transport processes. Free corrosion in different concretes is studied in terms of ambient relative humidity. The numerical results obtained by the finite volume method are discussed and compared with a reported experiment performed on a carbonated concrete.