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Vinod Kumar R&D Centre for Iron & Steel, Steel Authority of India Limited RANCHI - 834 002 (BIHAR) INDIA

CONTENTS 1. 2. 3. 4. Introduction Reinforcement Corrosion Mechanism of Reinforcement Corrosion Preventing Reinforcement Corrosion 4.1 Corrosion Resistant Rebars 4.1.1 Micro Alloyed Rebars 4.1.2 Low Alloy Rebars 4.1.3 High Alloy Rebars 4.1.4 Dual Phase Rebars 4.2 Protective Coatings 4.2.1 Metallic Coatings Sacrificial Coatings Passive Film Forming Coatings 4.2.2 Organic Coatings Epoxy Coating Polyurethane Coating Polymer Resin Coating 4.2.3 Cement-Slurry Coating 4.3 Cathodic Protection 4.3.1 Anode Cathodic Protection 4.3.2 Impressed Current Cathodic Protection 4.4 Electrochemical Removal of Chloride Ions 4.5 Concrete cover 4.5.1 Crack Width 4.5.2 Mix-Ratio 4.5.3 C170H- Ratio 317

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Vol. 16, No. 4, 1998

Protection of Steel Reinforcement for Concrete A Review

4.5.4 Additives Inhibitors Fly Ash 5. Concluding Remarks 6. References

ABSTRACT remature failure of reinforced concrete structures occurs primarily due to early corrosion of steel reinforcement These reinforcements are prevented from corrosion by the formation of a passive oxide film in the high pH environment of concrete. However, pH decreases in actual conditions due to the ingress of harmful ions like carbon dioxide, sulphur dioxide, chloride, etc., leading to localised corrosion. Of these, chloride ions are considered to be the most harmful, which may come from the deliberate additions of calcium chloride in the cement as accelerator or from the environment (marine/coastal regions, de-icing salts). The corrosion products thus formed, being more voluminous, result in expanded pressure in the surrounding concrete, leading to cracking of the concrete. The formation of such cracks accelerates further corrosion. In view of the intensity of the problem, serious efforts have been made to prevent corrosion of reinforcement These have led to the development of varying types of prevention techniques/measures including coatings, electrochemical techniques like cathodic and anodic protection, inhibitors, control of concrete mix and reinforcement with superior corrosion resistance. These preventive techniques have inherent advantages and disadvantages with respect to the type of structure and the surrounding environment. It is generally agreed that good concrete cover in terms of quality of ingredients, mix proportion, water-cement ratio, etc., has no substitute for the prevention of reinforcement corrosion. However, corrosion takes place due to the presence of fine cracks in the concrete assisting in the ingress of harmful ions. This necessitates an alternative preventive technique/measure which can be selected based on the type of structure to be protected, life expectancy, nature of environment, and cost of application. The present review provides an understanding of the process of reinforcement corrosion, its mechanism, different protection techniques being adopted or under development and their comparative analysis. 318
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Vinod Kumar

Corrosion Reviews

KEYWORDS Reinforcement, concrete, chloride ion, corrosion resistant rebars, stainless steel, galvanized steel, organic coatings, epoxy coating, polyurethane coating, polymer resin coating, cathodic protection, electrochemical removal, mix-ratio, Cl'/OH" ratio, inhibitors, fly-ash

1. INTRODUCTION Premature failure of steel-reinforced concrete structures has been one of the major problems confronting civil engineers. The reinforcement used to provide strength to the concrete structure, in most cases, is found to be the main culprit. This is primarily due to early corrosion of steel reinforcement A number of methods and materials have been developed or are being developed to prevent corrosion of reinforcement steel. This paper reviews the work carried out so far on reinforcement corrosion, its mechanism and prevention.

2. REINFORCEMENT CORROSION The reinforcement bars used to strengthen concrete structures are prevented from corrosion by the formation of a thin, adherent passive oxide film in the high pH environment of concrete /1,2/. The high pH (usually 12.5 to 13.5) is achieved by the formation of calcium hydroxide during hydration of cement. This high basicity level is good enough to maintain and protect the oxide film for a sufficiently long time. However, the presence of carbon dioxide and moisture in the environment gives rise to the formation of a weak carbonic acid which reacts with the calcium hydroxide in the concrete mix and forms calcium carbonate, thereby lowering the pH and in turn its passivating ability /3/. Passivity may be lost if pH falls due to carbonation to the range of 10.5 - 11.2. Calcium carbonate deposits in the pres of the paste and, since it occupies a greater volume than the hydroxide, the initial effect is partially to block the pores and give a denser paste. However, if the reaction goes to completion, pore water pH is reduced to 8.3 and certain products of hydration in the paste, notably basic silicates, basic aluminates and basic ferrites, become unstable and may begin to decompose. The steel no longer
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Vol. 16, No. 4, 1998

Protection of Steel Reinforcement for Concrete A Review

remains passive and with the availability of oxygen and moisture it is open to the corrosion process IM. However, it has been observed that lowering of the pH of the concrete cover due to carbonation is not beyond 0.5 inch and, therefore, if the cover thickness is less, this may destroy the passivefilm151. In addition to this, a more serious problem arises with chloride ingress, particularly in coastal regions, since even in concrete with low permeability, chlorides in the marine environment or sea water can penetrate at a much faster rate well beyond the usual depths of concrete cover within a time shorter than the life time of the structure /4/. Pitting corrosion caused by the chlorides is most harmful. The chloride ions are able to destroy locally the passivated film even in an uncarbonated concrete cover. A very small anodic surface is then facing a larger cathodic surface still coated with the passivating layer. These unfavourable surface conditions cause highly accelerated and deep corrosion penetration into the steel. Chloride is used in an intermediate chemical reaction but in the end it is not consumed and acts as a permanent catalyst in the corrosion process. Furthermore, the hydrochloric acid simultaneously formed reduces the pH value at the corrosion pit. If the steel reinforcement is corroded by chloride penetration, then no superficial remedial treatment is available at present. The only possible solution is to replace the steel or rebuild it after demolishing the element /4/. Chloride ions may come from the deliberate addition of calcium chloride to the cement as an accelerator, or from the environment (the presence of chloride ions in marine/coastal regions or from de-icing salts). The combined effect of carbonation and the presence of chloride can provide a very corrosive environment for the embedded steel. The corrosion products thus formed are more voluminous than the parent material /2/; their formation and deposition on the bars results in expansive pressure in the surrounding concrete leading to cracking of the concrete. Obviously, the formation of such cracks accelerates further deterioration 161. Other factors may also combine to aggravate this situation. For example, a reinforced concrete structure at a liquefied gas/sulphur plant in the Arabian Gulf deteriorated shortly after completion of the construction 111. Investigations revealed that the primary cause for this was corrosion of reinforcing steel due to the presence of chloride available from marine salt combined with an increased level of industrial pollutants. Other contributing factors included the use of sulphite-resisting Portland cement, the presence of hairline cracks in the concrete, the elevated water/cement ratio, and insufficient 320
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206. This was aided by simultaneous action of multiple environmental factors.138 Download Date | 11/20/12 9:22 AM . high relative humidities and air temperature. the reinforcement remains unattacked under a highly alkaline environment (pH > 1 3 due to the presence of sodium and potassium hydroxide Ι9Γ). MECHANISM OF REINFORCEMENT CORROSION /8/ As discussed earlier. The foregoing reaction products lead to the precipitation of hydroxides according to Fe"" + 20H" 2+ Fe(OH) : 2Fe(OH)3 (4) (5) 2Fe(OH)2 + V2O2 + H 2 0 321 Unauthenticated | 117.15. unfavourable wind speed and direction. epoxy coating. steel passivates in the presence of oxygen by the formation of a surface layer of Fe203. 3. and corrosive ground conditions. such as the high salinity of Gulf water with a consequent high-rate fallout of marine salts. This is due to the fact that. or the passive oxide film The anodic reactions leading to the dissolution of iron are: Fe — Fe 2+ + 2e~ > (2) The rate of corrosion is affected by oxygen transport through the concrete cover to the steel where cathodic reduction l A0 2 + H 2 0 + 2e~ -h> 20H" (3) can sustain the corrosion process /11. at this pH. which limits corrosion rate to that required to maintain passivity by the following anode reaction HOL 2Fe + 60H" -> Fe 2 0 3 + 3H 2 0 + 6e~ (1) The corrosion of reinforcement generally takes place by the formation of galvanic cells in which the parent metal acts as the anode. intense solar radiation. The cathode may be mill scale.Vinod Kumar Corrosion Reviews concrete cover.12/.

At low potentials the anode reaction may /15. Oxygen access to the steel may become so limited that the passive current cannot be sustained and general depassivation occurs /15/. can change both the concrete and its pore solution chemistry. if the concrete is fully saturated with sufficient depth of cover /12/. hematite (Fe203). e. 16.16/ be the formation of Fe(OH)2 Fe + 20H" Fe(OH). and the composition of rebars /13/. The rate of corrosion is then limited by diffusion of oxygen or the kinetics of water reduction 2H 2 0 + 2e~ ->· 20H~ + H2 (6) This type of corrosion is characterized by low potentials. and. leading to depassivation of the reinforcement /10/. where Ecorr is more negative than -800 mV (SCE). oxygen availability is restricted. 1998 Protection of Steel Reinforcement for Concrete A Review The hydrated oxides in concrete can convert to various oxide species. + 2e" (7) Under strongly alkaline conditions the formation of soluble FeO(OH)" is feasible /16/. 4. leading to a complex system of compounds depending on pH.15. Ingress of aggressive species. even in well oxygenated waters.206. FeOOH is more adherent to metal substrates than Fe20 3 and Fe 3 0 4 /14/. acidic gases /19/. No. therefore. oxygen availability. but only at low concentrations. It can occur. could slow the corrosion rate at the interface between the oxides and the metal matrix. such as magnetite (Fe 3 0 4 ).Vol. chloride ions or carbon dioxide. or immersed in sea water 1201. Corrosion in the Presence of Chloride l l l l The degree of protection provided by concrete may be reduced when a reinforced structure is exposed to de-icing salts /18/. therefore. In buried or fully saturated reinforced concrete.g. this reaction is balanced by cathodic reduction of dissolved oxygen to hydroxyl ions (OH)": 322 Unauthenticated | 117. accelerating the corrosion where metallic Fe at the anode is oxidized to ferrous ions (Fe24): Fe Fe :+ + 2e" (8) Initially.138 Download Date | 11/20/12 9:22 AM . and. and geothite (FeOOOH).

H 2 0).206. expansive stresses due to corrosion products may lead to cracking and spalling of the concrete /21/.138 Download Date | 11/20/12 9:22 AM . Ionic Diffusion The diflusion of chloride ion through the concrete cover can be estimated by using Fick's second law of difiiision.H 2 0): 4Fe(OH) 2 + 0 2 -> 2 H 2 0 + 2Fe 2 0 3 . 323 Unauthenticated | 117. H 2 0 -> H 2 0 + Fe 3 0 4 (12) (13) (14) A tubercle is formed at the pit orifice.Vinod Kumar Corrosion Reviews 0 2 + 2 H 2 0 + 4e" 4(0H)" (9) The Fe2+ combined with CP drive to the anode by the corrosion current and form the H 2 0 soluble ferrous chloride (FeCl2): Fe 2+ + 2C1" -> FeCI2 (10) Some FeCl2 migrates out of the corrosion pit and reacts with the cathodically formed sodium hydroxide (NaOH) to produce a ring of a white precipitate of ferrous hydroxide Fe(OH)2: FeCl. and to black magnetite (Fe3O.0. This tubercle hinders the replenishment of dissolved 0 2 into the pit interior and prevents intermixing of the electrolyte trapped inside the pit with the bulk solution resulting in local acidification. This type of localized attack.15. Apart from strength loss. followed by the formation of green hydrated magnetite (Fe 3 0 4 .H 2 0 F e 3 0 4 . which consists mainly of Fe 3 0 4 and Fe 2 0 3 . can cause structural damage.H 2 0 6Fe(OH) 2 + 0 2 ^ 4 H 2 0 + 2Fe 2 0 3 . when coupled with a large passive area of reinforcement.H 2 0. + 2NaOH = Fe(OH) 2 + 2NaCl (11) The Fe(OH)2 is soon converted to hydrated ferric oxide (Fe 2 0 3 . also known as ordinary red-brown rust.

4. since such defects provide preferred diffusion pathways for both reactants and products. D. of chloride ion through sound concrete has been reported to be 10"7 ~ 10-8 cnm2/sec 1221. the pore solution will lose hydroxide ions and acquire chloride ions through ionic diffusion. Ionic and molecular transport in a hardened concrete will depend upon the physical characteristics of the mix /8/. over 10 years would be required for chloride ions to reach the rebar surface by diffusion through a concrete cover of 28mm. and thus it is only a matter of time before sufficient chloride reaches the steel and pitting occurs. For boundary conditions: c = 0 at t = 0 (0 < χ < c/ce = 1 . Inhomogeneity can also result from local variations in the mix during placement and subsequent cement hydration.24-26/. but experiments /23/ showed it to be only 0. whereas most concrete placed in real structures is unlikely to be homogeneous /15/.12. and ce is the concentration at equilibrium (10%). Cement composition influences both the rate of chloride diffusion and the ratio of bound-to-unbound chloride /24-27/. Diffusion coefficient.25 year. In sea water. Measurements of ionic diffusion and oxygen transport have concentrated homogeneous pastes under "fully water saturated" conditions. t. x. This was possible because micro-cracks in concrete cover might have facilitated the diffusion of chloride ions by an order of magnitude. For example.138 Download Date | 11/20/12 9:22 AM .erf(x / 2VDt) c = c e at χ = 0 (0 < t < ») (16) (17) Based on the above equations.15.206. No. from the surface at a time. the diffusion rates for oxygen and chloride are reduced when porosity is decreased by lowering the water/ordinary Portland cement (w/c) ratio /11. Areas of reinforcing bar corrosion are often associated with cracks and voids /15/. 1998 Protection of Steel Reinforcement for Concrete A Review (15) where c is the concentration of chloride ion in concrete at a distance.Vol. Gjorv and Vennesland suggested that a dense cement-rich layer on the cast 324 Unauthenticated | 117. 16. Interfacial Layers (Cement/Environment) /8/ Surface layers can affect transport processes in concrete and cement.

which limit subsequent Mg2"1" ingress and increase resistivity /28. Interfacial Layers (Steel/Cement) /8/ Page III identified a layer of Ca(OH)2 (Portlandite) precipitated on steel cast in hardened cement and proposed that this could act as a barrier to chloride ions. Seawater exposure causes precipitation of CaC0 3 (Aragonite) and Mg(OH)2 (Brucite) layers in the surface pores of hardened cement. even at low C170H . whereas civil engineers developed better understanding of concrete control.30. Kumar 133/ observed that any preventive method in isolation may not be sufficient and a combination of preventive methods may be needed to protect the reinforcement from corrosion. metallurgists or materials scientists developed corrosion resistant rebars and metallic coatings. thorough analysis is needed of various preventive methods.206. electro-migration of these ions can evolve an environment that is locally acidified and concentrated in chloride. which produces local depassivation 1321. He 1331 explained this by comparing a RCC (Reinforcement-Cement-Concrete) structure with a king's fortress where the king employs a number of security measures to protect his 325 Unauthenticated | 117.31/. Therefore. Defects in this layer could lead to pitting /1.Vinod Kumar Corrosion Reviews surfaces of concrete increases its resistivity /26/ and limits oxygen diffusion /11/ to a greater extent than an equal thickness of mortar. chemical engineers or chemists developed organic coatings.15. These efforts led to the development of a number of preventive methods which are quite different from each other.ratios in the pore solution. The Ca(OH)2 in the hardened concrete appears to have a dual role. PREVENTING REINFORCEMENT CORROSION Researchers from different disciplines have tried to develop different preventive methods based on the experience related to their field For example. thus protecting passive steels. their advantages and disadvantages. though each one of them is claimed to be the most effective solution to reinforcement corrosion by the respective investigator. However.29/ by modifying the pore size distribution There is evidence that these layers may also reduce oxygen transport /15/ and may be beneficial in repairing cracks.138 Download Date | 11/20/12 9:22 AM . providing both a physical barrier layer and a reserve of alkalinity to resist local acidification 4.

Corrosion Resistant Rebars In recent years.206. use of an electrochemical technique. 4. The environment (electrolytic solution) provides a way for electron as well as metal-ion transfer. Each of these methods is discussed in detail in the following sections. The rate of corrosion can be restricted by the absence of any of these three. 326 Unauthenticated | 117. No. Since corrosion is an electrochemical process. Ni.15. The rates of both the anodic and the cathodic process are always equal. Various types of corrosion resistant rebars currently being used are discussed in the following sections. Production of these rebars does not require any additional facility / capital investment and manpower as in the case of various coated rebar and cathodic protections and. it involve a cathode. or by regulating them The corrosion of reinforcement can be prevented by (i) (ii) (iii) (iv) use of corrosion resistant steel rebars. Low-Alloy Steel Rebars /37-48/ Alloying elements like Cu.138 Download Date | 11/20/12 9:22 AM . are added for this purpose. but under highly alkaline conditions the rust formed becomes adherent and protective so that corrosion becomes less rapid than with ordinary steels. etc. Nor does this call for any design changes. P. 4. an anode and a suitable environment The corrosion takes place at the anode and simultaneous reduction of hydrogen or hydrogen evolution takes place at the cathode (in the case of an acid solution) or hydrolysis of water giving rise to hydroxide ions (in the case of a highly alkaline solution). however. other alloys have also been added along with chromium. 4. These developments have been based on (i) alloy additions and/or (ii) microstructural control.2. the cost of protection is much lower. therefore. A combination of preventive methods may be selected based on the severity of corrosion and the extent of protection needed. Cr. 1998 Protection of Steel Reinforcement for Concrete A Review kingdom. 16.1.1. Chromium has been the common choice by most of the researchers. use of a protective coating on the rebar. and control of concrete mix.Vol. efforts have been made to develop corrosion resistant rebars to prevent reinforcement corrosion (Table 1). This is due to the fact that Cr makes the iron oxide more dense and adherent These steels still rust. W.

0.138 Download Date | 11/20/12 9:22 AM . Dual phase 56 SAIL has also developed both cold twisted deformed (CTD) as well as thermo-mechanically treated (TMT) rebars /38-41/ having superior corrosion resistance compared to conventional rebars.3.5% Microalloy — Unalloyed ** Not available. 1.0-5.Vinod Kumar Corrosion Reviews Table 1 Corrosion Resistant Reinforcements Rebar Quality Microalloyed steel Low-alloy steel Alloying Elements Microalloy Cr Cr + Cu Cr + Cu + Ρ Cu + W Ni Ni + W Cr Stainless steel Al + Cr + Cu/Ni + Ti/Nb/Mo/V/W/Cb/B (Non-magnetic steel) Addition ** Reference s 34-36 37 38-41 42-44 45-4.01-0.3% maximum to achieve high strength.3% Al 5.206. High-Alloy Steel Rebars /49-55/ These rebars belong to the stainless steel category where alloy additions are made in excess of 12%.15.5% Cu/Ni 0. Microalloying may be done up to 0.0-37. 4.75% min.50 -10. These rebars belong to high strength grades (yield strength in excess of 415 MPa) of IS: 1786-1985. Both ferritic /49.65 46.5%W 12% Ferritic Austenitic 20. ** High-alloy steel 3.0% Cr 0.50/ as well as austenitic stainless 327 Unauthenticated | 117. TMT rebars are weldable due to their low carbon equivalent The low-alloy steel rebars are a cheaper option because of low alloying additions.62% max.001-0.47 48 49 50 51-53 54 55 2% 0.5% 1. Shimada and co-workers /46-48/ have found that nickel additions are most useful for improving salt corrosion resistance.1 -5.5%Ni.1.

4. McDonald et al. by shot or sand blasting or by pickling in inhibited acid solutions. if we are to use stainless steel or 328 Unauthenticated | 117. 16.15. 4. such as magnetic floating high-speed railways. Non-magnetic steels having superior corrosion resistance have also been developed for use in various concrete structures. Novak et al.4wt%/cement) and is not suitable for high chloride concentration /58/. show only negligible reduction in tensile strength and yield strength when exposed for two hours at 600°C.Vol.4. prerusted) on the corrosion rate and found that the prerusted reinforcement embedded in concrete showed the highest and technically unacceptable corrosion rate under all conditions. Callaghan 754/ has also suggested that. Cochrane 1521 observed that only austenitic stainless steel (Type 304) was wholly serviceable in the high chloride concentration (3. Dual Phase Steel Rebars 1561 This steel consists of martensite and ferrite produced by controlled processing. 1531 have shown that the use of austenitic stainless steel for the reinforcement of concrete bridges would add between 6% to 16% cost to the structure. 152. nuclear fusion facilities and marine structures and appliances where non-magnetic properties are required in addition to corrosion resistance /55/. No.138 Download Date | 11/20/12 9:22 AM . Rust/mill-scale can be removed by weathering.2% chloride ion equivalent to 5% by weight of cement) whereas ferritic stainless steels (Types 405 and 430) were affected by the same chloride concentrations. 1998 Protection of Steel Reinforcement for Concrete A Review 1521 steels have been used for reinforcement purposes. besides showing superior corrosion resistance properties. It is reported that the corrosion rate of originally rusted steel rebar was two times higher than that of pickled steel /57/. The scaled surface was comparable to a rust-free machined surface. The last method is preferred. has a corrosion rate acceptable for low chloride contents (0. The superior corrosion resistance has been derived based on the small potential difference between ferrite and martensite as compared to a large potential difference between ferrite and martensite giving rise to galvanic corrosioa All reinforcements should be free from mill-scale or corrosion product. It is reported /54/ that stainless steel rebars. Care must be taken that the acid is properly inhibited and that the correct concentration of inhibitor is maintained throughout the pickling period. but should only be undertaken by an experienced staff. scaled.1 have also studied the different states of surface of rebar (machined.1. including concrete without chloride content.206.

However.2. fabrication. it is essential that all scale or scale formed before and during bar deformation be removed. like moderate-to-severe exposures.1.84. in general). He /54/ found that the presence of mill scale or hot rolled scale resulted in early signs of corrosion in 12%Cr steel and led to the initiation of pitting corrosion in type 316 and type 304 steels.206. This has led to the wide-ranging research on galvanized steels /61-92/ compared to others /80.g. Al-Tayyib et al. It may lead to localized attack. galvanizing. two broad types of coatings have been developed. e. water treatment and chemical processing facilities. cadmium and zinc were anodic to steel as 329 Unauthenticated | 117. etc. corrosion prevention is based on a sacrificial anode compared to the cathodic underlying parent metal. and.93-100/.2. even if the coating is broken due to the above-mentioned reasons. they be pickled and passivated or abrasive-blasted. power generation facilities. 1601. Cr-based coatings. The first option is based on a passive Film formation and its adherence to the rebar. tin and lead were cathodic to steel. copper. industrial plants.138 Download Date | 11/20/12 9:22 AM . the metal remains protected. e. in the second option.g. therefore. It should be noted that the parent metal acts as an anode compared to the cathodic passive film. Si-based coatings. tin. 4. However.15. Coated reinforcements are also used in less severe applications in building and construction for cast-in-place and precast elements. transportation. and (ii) sacrificial coatings. Lead. if broken during service. such as marine and coastal construction. i.Vinod Kumar Corrosion Reviews the 12% Cr steels. Coated steel reinforcements have been widely used in many areas. Protective Coatings The use of coatings for corrosion protection of structures has already been presented in detail by Giudice et al. In view of this. Different types of coatings suitable and unsuitable for rebar are included in Table 2 and are discussed in detail in the following sections. 4. nickel. These are (i) passive film-forming coatings. 1591 have shown that the initial rusting does not have an adverse effect on the corrosion resistance of rebars embedded in concrete. A scrutiny of the potential values against SCE (Saturated Calomel Electrode) suggests that only cadmium and zinc can provide galvanic protection to the steel under normal environmental conditions (Table 3). In seawater. and bridges and highways.e. Metallic Coatings The development of metallic coatings was based on their role as regards corrosion in combination with the parent metal (mild steel.

No.040 -0. but the rates of self-corrosion were relatively higher 19. brittle.760 -0. subject to cold flow. intolerant to poor surface preparation Neoprene Poor bond Vinyl No concrete to vinyl bond Aluminium No electrical insulation effect.795 long as pH remained strongly alkaline.180 -0.484 +0.636 -0.490 -0.830 -0.9% Sea Water -0. These potential values can serve as reference for selecting a coating metal for a particular environment 330 Unauthenticated | 117.650 -0.210 -0.980 -0. no electrical insulating effect Nickel/copper Not suitable for chloride exposure. 1998 Protection of Steel Reinforcement for Concrete A Review Table 2 Different Types of Coatings for Steel Rebar 7137/ System Disadvantages Coatings not suitable Red lead Deterioration in alkaline medium Coal tar enamel Brittle. rapid corrosion in presence of chloride Coatings suitable Zinc/cadmium Sacrificial.450 Mortar containing 1% NaCl -0. sticky Asphalt Subject to cold flow Deterioration in alkaline medium Phenolic Urethane Hard.01.370 -0.138 Download Date | 11/20/12 9:22 AM .Vol. galvanic corrosion Epoxy Hard and brittle. 4.200 -0.010 -0.206.760 -0.510 -1.720 -0.360 -0.870 -0. rapid corrosion in the presence of chloride. Only powder epoxy suitable.200 -0.674 -0.140 -0. no electrical insulating effect. Chlorinated May bond to both concrete and steel rubber Table 3 Potential Values Against SCE 783/ Metal Normal Nickel Copper Steel Tin Cadmium Lead Zinc -0.15. 16. In many formulations will not bend or stretch Many formulations have poor bond. V Mortar +0.060 Potential.210 -0.110 -0.450 -1.

Griffen /70/ observed that galvanized steel has no advantages when exposed to marine conditions. however. found that galvanized steel resists higher chloride concentrations than bare steel in saturated Ca(OH)2 solutions with additions of NaCl from 0. the metal remains protected. Ishiwaka /71/. however.5). Experience /66-68/ showed that the use of galvanized steel involves an improvement in durability of the structures when they are in contact with chlorides. Galvanized reinforcement has been in use since the 1930s and is used in many types of concrete constructions /61. Unz /69/ studied both galvanized and non-galvanized steel plates. and found that the galvanized 331 Unauthenticated | 117. transportation or fabrication. Other authors also supported this finding Z72-74/. resist mechanical damage.1.5) than that which causes corrosion of black steel (pH <~11. Zn is passivated in concrete and can remain passivated to lower pH levels (perhaps as low as pH 9.15. simulating an aqueous phase present in the concrete pores. Because the steel is hot-dipped into molten Zn at « 460°C. Various studies. totally or partially immersed in Ca(OH)2 saturated solutions with additions of NaCl. Marias and co-workers /75-78/ have carried out an extensive study on the behaviour of galvanized steel in alkaline solutions.62/.2. Therefore. and afford sacrificial protection to the steel 1631. Mange /65/ found that galvanized steel showed bad behaviour in structures in contact with chlorides where water retention and temperature were aggravators of the corrosion process on reinforcement. Galvanized reinforcement also can withstand exposure to chloride ion concentrations several times higher than that which causes corrosion of black steel in concrete /64/.206.Vinod Kumar Corrosion Reviews 4. Sacrificial Coatings Corrosion prevention is based on a sacrificial coating which acts as an anode compared to the cathodic underlying parent metal. The alloy layers are strong. and found that galvanic currents produced in non-uniform exposure conditions lead to local accumulations of chlorides with intense pitting corrosion. have not shown total agreement on the corrosion resistance of zinc in concrete environment as in other aggressive media. galvanizing produces a metallurgically alloyed coating integrally bound to the steel substrate.138 Download Date | 11/20/12 9:22 AM . This lack of clarity is largely based on the fact that hardened concrete is a complete electrolyte for the study of metallic corrosion processes. even if the coating is broken/removed during service. though their respective results differ as to the minimum chloride concentration needed to provoke pitting corrosion.1. Galvanizing thus offers substantial protection against the effects of carbonation in concrete.0%. independent of the existence of passivating films.2 to 2.

serious rusting will be delayed. however.5 times the level that caused corrosion of black steel. Ca(Zn(0H)3)2. 1998 Protection of Steel Reinforcement for Concrete A Review steel becomes passivated in contact with electrolytes whose pH value is < 13. it was confirmed that the passivation product of the galvanized steel in these media was calcium hydroxyzincate.206. Zinc provided sacrificial protection for a period of »4 to 5 times that for initiation of corrosion of black steel in equivalent conditions. the Ca2+ ions have a certain buffering effect and the pH value remains inside a narrow range around 12 /78/. 16. Yeomans /80/ alsop studied the performance of black (uncoated). 1 and that above this value the galvanized coating is completely dissolved until it totally disappears within a period shorter than 33 days. CaCl2 or NaCl. the onset of corrosion is deferred. In another study. 332 Unauthenticated | 117. but for CaCl2. and long-term protection is provided to the reinforcement prior to its being embedded in concrete.138 Download Date | 11/20/12 9:22 AM . As far as bond strength of galvanized bars is concerned. which remain protective after the zinc coat itself has eroded away.3 ± 0 . The latter hardly alters the medium pH.2H20 /7577/. With wellgalvanized steel it is usual to consider that as long as 10% of the original coat remains. but also to the fact that if the steel is properly galvanized.15. observed that galvanizing is not a substitute for good concrete technology. it is equivalent to that of uncoated bars. The nature and thickness of the alloy layers are influenced by the composition of the underlying steel and by the galvanizing conditions. Subramanian /84/. 4. The presence of carbon and silicon in the steel encourages the formation of iron/zinc alloys and thus leads to the formation of heavier coats. which depends on the calcium or sodium salt. Treadaway /79/ found that galvanized reinforcement offers several advantages over black steel. but owing to the sacrificial protective action of the zinc. Steels with a high silicon content are often used when very thick coats of galvanization are required. galvanized and epoxy-coated reinforcing steels in chloride-contaminated concrete and found that galvanized steel resisted CI" levels in concrete «2.Vol. Similarly. the risk of cracking and rust staining is reduced. which provides the chloride ions. The useful life of a zinc coating largely depends on the thickness of the coat. This is due not only to the sacrificial action of the zinc coat. No. a large amount of coating can be lost before the underlying metal is attacked. a series of protective alloy layers forms at the iron/zinc interface. In particular. /78/ have confirmed that the corrosion behaviour of galvanized steel in the presence of chlorides is controlled by a medium pH. Marias et al. variability in the concrete mass (such as depth of cover to the reinforcement and gross porosity) can be tolerated better.

Organic Coatings Organic coatings include epoxy coatings. 4. to a large extent. Ti-Ni and Si-Ti which can be applied by fluidized bed chemical vapour deposition (FBR-CVD). Epoxy Coating Fusion-bonded epoxy coated reinforcement (FBECR) was developed between the late 1960s and the early 1970s /101/ in respect to severe rebar corrosion problems in bridge decks in North America.1. fabrication. They /94/ also showed that the best coatings were obtained when Si and Ti were co-deposited at temperatures around 550°C. Tomlinson et al. and epoxy coating is clearly the dominant coated reinforcement in general use /102-108/. Passive Film Formine Coatings As discussed earlier. polyurethane. These include: Si. Titanium was very corrosion-resistant Tin was found to be highly resistant to pitting and the small amount of dissolution can possibly be reduced. Sanjuro et al. Of these. All these coatings act as a barrier to the aggressive ions. or FBR-plasma spray techniques. it has problems of toxicity /100/. In addition. It may lead to localized attack. Cd.2. 4. less expensive Si-coated samples resisted scratching 1921.Vinod Kumar Corrosion Reviews 4. polypropylene. Epoxy coatings provide excellent corrosion protection to steel. Ni. polyvinyl chloride. etc. epoxy coatings have been most popular.2.2. paint-and-heat. These coatings increased the corrosion resistance by more than an order of magnitude with respect to the uncoated rebars.1. Ti.138 Download Date | 11/20/12 9:22 AM 333 . Of these. moisture and oxygen and remain cathodic with respect to the steel. and the coating is not consumed in performing its corrosion protection function Unauthenticated | 117. phenolic nitrite. /95/ showed that the Si-coated samples indicate a higher corrosion resistance in aggressive chloride environment in comparison to fusion-bonded epoxy coated or galvanized bars.2. and was first used in 1973 for the same purpose /80/.206. transportation. this is based on a passive film formation and its adherence to the rebar. by alloying. It should be noted that the parent metal acts as an anode compared to the cathodic passive film. Mg.15. if broken during service. /100/ have shown that Ni and electroless nickel were very stable in the passive range and the electrolytically induced pitting is not considered important in service.2. etc. the paint-and-heat process appears most suitable for commercial application /93/.2. Although Cd had excellent corrosion resistance. Magnesium was not found suitable since it corroded readily. Its use is now varied and widespread.

the effectiveness of epoxy coatings in veiy aggressive environments has recently been questioned /113-115/.2H 2 0 with and without 0. alternatively. that the corrosion-free service life in these structures will primarily be the result of concrete quality and thick cover. primarily because the coating has naturally occurring holidays /116/ and may be damaged during transportation and fabrication Consequently. 16. The exposed steel then corrodes as an anode driven by the relatively large cathode of surrounding passive steel. Sagues /116/ has also observed. Hence the steel surface is protected. and not will not necessarily be due to the use of epoxy-coated rebar. and. the local concrete alkalinity is reduced by carbonation of concrete. Allowance must be made for some normal damage to the coating during assembly and concrete casting The steel can corrode at any hole in the coating. The coating has veiy low permeability to chloride ion. No. a great deal of emphasis is placed on the careful handling and storage of epoxy-coated reinforcement to minimize abrasion and mechanical damage /117/. but the extent of corrosion is controlled by the surrounding intact epoxy layer which stifles the cathodic reactions and prevents macro-cell corrosion. An epoxy coating on steel acts as a veiy effective barrier to aggressive agents.Vol. and is essentially unaffected in many environments. after inspection of over 30 bridges. the corrosion of the steel in the vicinity of the hole is 10 to 100 times less than it would be for uncoated reinforcement Despite the excellent corrosion performance of epoxy-coated reinforcement in most situations. The steel surface at the hole has to sustain both the anode and the cathode. 3M NaOH aqueous solution. Corrosion of uncoated reinforcement is attributed to the local loss of the passive surface film locally when chloride ions penetrate through the cover concrete. particularly chloride ions. 4. Muthukrishnan et al.138 Download Date | 11/20/12 9:22 AM . is highly chemically resistant. because the cathode reaction is much less efficient than the anodic reaction.15. Touch-up of damaged areas of the coating is usually required. saturated Ca(OH>2 and CaS0 4 . /83/ have shown that only epoxy coatings (both liquid and powder) were not affected when tested for one year in 3M CaCl2 aqueous solution.5M CaCl2.206. Pitting results and is referred to as macro-cell corrosion. Hartley /101/ has presented the protection of rebar by FBECR. which will not easily diffuse through a continuous epoxy coating. 1998 Protection of Steel Reinforcement for Concrete A Review /109-111/. FBECR is specified to improve resistance of concrete structures to 334 Unauthenticated | 117. The presence of epoxy coating on FBECR acts as a barrier to chloride ions and prevents corrosion.

A comparison of the performance of typical systems as regards their concrete resistance in various environments is given in Table 4. there is the widest diversity of compositions of polyurethane which can be designed to suit every requirement Polyurethanes are grouped into six types according to the method of curing. bond strength is reduced by the smooth surface of the epoxy coating. wet-therapy rooms. warehouses. Recently. Also. kitchens. differential shrinkage built up in the polymer during curing and early weathering which is aided by UV radiation. The reductions are approximately 15 25% /117/.2 Polyurethane Coatinz This coating method has been developed to overcome disadvantages accompanying thermosetting type polymers like epoxy. including Chromate and non-chromate surface treatments and coatings for prefabricated rebar.2. temperature and pH /118/. attention in the epoxy-coated rebar industry has focused on service in hot/wet environments. as per ASTM D-16 classification Of these. 4. Polyurethane coatings are considered to be bacteriostatic since they do not provide nourishment to bacteria In moist and warm conditions. thickness of the coating. New specifications mandate quality control programs that include cathodic-disbondment testing /118/. A typical example is the simultaneous exposure to chemicals and abrasion that occurs in store rooms. These are a build-up of thermal stress in the polymer during curing. essential that the concrete beneath the coating is strong enough to take the loads without crumbling /II9/. The factors affecting cathodic-disbondment are application temperature. type V is the best choice as given in Table 5. a number of systems are now available.138 Download Date | 11/20/12 9:22 AM 335 . Pathare /119/ observed that polyurethane coatings can be devoid of the above defects if the proper choice is made. Unauthenticated | 117. weight of treatment applied. poor film-forming capacity and a marked tendency to form pinholes and pores causing non-conductivity in the film. Various authors have recommended reductions in design bond strength based on comparisons of performance of epoxy-coated and noncoated bars under identical conditions.2. It is. To meet this requirement. oxygen. testing time.Vinod Kumar Corrosion Reviews corrosion. This is the reason why they are especially recommended for floors where the usual types of laid floor coverings are unable to meet the requirements of particularly severe stresses. however.15. however.206. etc. Polyurethane coatings have particularly high resistance to abrasion and wear. steel surface preparation and contamination. heat and moisture /119/.

Of these. electronic. No. 16.2.206. Therefore. methyl-silicone polymer or acrylic rubber separately or cojointly on the reinforced concrete surface. (iii) toxic effect of metabolic products of fungi (mycotoxins. (ii) hygiene is reduced since fungus-contaminated areas can be dangerous sources of infection. 4. 4. (iv) destruction of the wall coatings or coverings. and (v) destruction and rotting of the plaster and subsequent destruction of concrete /119/.8 4 A lira sion 8 Heat Biodegr adation 7 3 5 8 8 4 7 9 10 Acrylics Alkyds Bituminous Chlorinated Rubber Epoxy Epoxy ester Phenolic Silicones Polyurethane (aliphatic) 8 6 10 10 9 5 10 4 9 8 6 7 9 10 5 "> 8 8 10 9 10 7 10 6 10 8 7 8 8 10 7 10 8 10 7 8 4 6 7 7 7 10 8 ft 3 5 9 6 6 7 9 7 9 3 9 6 9 6 6 4 6 8 9 8 6 6 6 9 10 3 9 microflora form very quickly and spread by multiplication which is manifested as follows: (i) appearance is impaired.Vol.2.15. alfatoxins) even in very small concentrations. hospital and foodstuff industries. most of these effects can be eliminated.138 Download Date | 11/20/12 9:22 AM . The suppression of rebar corrosion involves cutting off the source of moisture followed by application of a highly durable waterproof coating of silane monomer. silane monomer coating provided the most effective characteristics of water barrier and corrosion suppressant /120Λ 336 Unauthenticated | 117. polyurethane coating is the ultimate choice for clean rooms in the pharmaceutical. With properly formulated polyurethane coatings. 1998 Protection of Steel Reinforcement for Concrete A Review Table 4 Comparative Performance of Topical Systems on Concrete Resistance to Various Environments / 119/ System Acid Alkali Salts Solve nts 5 4 Ί Water Oxid ation 8 3 UV Radiation 9 .3 Polymeric Resin Coating The use of an airtight protective coating of polymeric resin on the existing reinforced concrete surfaces would inhibit carbonation/120/.

138 Download Date | 11/20/12 9:22 AM 337 . • Similar to type IV which need mixing just Two-component before application. • May undergo drying reaction with traces of moisture under improper handling or storage much before the intended application and hence may fail to function. ponents heat cure Two-component • Solution of simple and linear polyurethane in catalyst cure solvent • Film is formed by evaporation of solvents on application and. • Polyurethane formation can occur directly on the surface to be coated after mixing the two components.• Not suitable for concrete. polyol/isocyanate cure • Best and more convenient than type IV.Vinod Kumar Corrosion Reviews Table 5 Characteristics of Various Types of Polyurethane Coatings 7119/ Type I Remarks • Oil urethane system • Oil or alkyds dry by air oxidation. • Improvements can be made by substituting oil or alkyds with diols or polyesters. Single component • Drying alkyds of their isocyanate function at the end of the linear polymer chain and this isocyanate portion of the polymer picks up atmospheric moisture and the film dries by formation of polyurea. One or two com.15. hence. Description Air drying π m rv V VI Unauthenticated | 117. • Unpredictable behaviour under humid tropic weather. • Choice of composition is limited and polySolvent evaporation urethane linkages are already formed. not advisable as a protective system on concrete. • Possible to make a choice of individual components as per properties of the coating desired (a distinct property of polyurethane). Catalyst only brings about cross linking of the two polymers. • Hardness of the film and film properties are slightly better than conventional enamel paints.206.

notably sodium dichromate /131/. sodium phosphate /132/. No. Bitumen paints are said to protect reinforcements from calcium chloride in concrete. either because of their doubtful field performance or their adverse effect on bonding. the inhibited and sealed cement-sluny coating has performed very efficiently by showing only negligible superficial rusting. The steel reinforcement embedded in concrete is surrounded by an alkaline medium. But none of these methods appear to have made much headway.134/ and also barium Chromate /135/. such as pickling in hydrochloric acid followed by treatment with phosphoric acid /125/ and treatment with a hydrolysable silicate or hydrated silica /126/. but some paints of this type revent the formation of bond between the steel and the concrete /130/. This entire procedure takes about three days /137/. 16. Wyatt /138/ has presented a review of the developments in 338 Unauthenticated | 117. They observed that even under the most aggressive macro-cell corrosion conditions. Inhibited Cement-Slurry Coating Due to the failure of epoxy-coated reinforcing steel in marinesubstructure service. The application procedure for cement-sluny coating involved derusting. which is again alkaline. interest has recently been revived in macro-cell corrosion studies /121-124/. The application of coatings of cement containing paints with water proofing admixtures /128/. Cathodic Protection Cathodic protection is currently becoming one of the most useful methods in conosion protection because it controls the electrochemical conosion process itself. sodium carbonate. Because of the surrounding concrete. Combinations of inhibiting agents in cement slurries are also proposed.137/ have shown that cement-sluny coated reinforcements were found to be three times more durable when compared to uncoated reinforcements under simulated macro-cell corrosion conditions.138 Download Date | 11/20/12 9:22 AM .Vol. Simple preliminary coating of steel with a dense mortar is recommended to counteract acid fumes /127/. and two coats of cement followed by sealing. /136. the galvanic effect is likely to be pronounced. 1998 Protection of Steel Reinforcement for Concrete A Review 4. a coating based on cement is expected to be more compatible. A cement coating is a passivating type of coating and may have higher tolerance towards defects.15. Various passivating treatments for reinforcement have been suggested. In a study.206. phosphating.3. sodium benzoate /133. or of slurries of lime and cement with casein or bone glue /129/ is also recommended as an anti-corrosive measure.2. 4. Rengaswamy et al. 4.3.

being electrically connected with the reinforcement. as well as the danger of hydrogen evolution in the high current zones /142/.c. One of the main criteria for effective cathodic protection is that the applied current should be uniformly distributed to the steel to be protected. Pithouse /141/ has studied both types of cathodic protection systems on concrete repair work and found that the current systems have been the most successful.144/ has developed a technique based on the use of a zinc wire as sacrificial anode along the length of a rebar.Vinod Kumar Corrosion Reviews cathodic protection of reinforced concrete structures. The cathodic protection method may be broadly classified into two categories: (i) sacrificial anode cathodic protection and (ii) impressed current method. Sacrificial Anode Cathodic Protection This preventive method is based on the use of a sacrificial anode which is consumed during corrosion and the reinforcement remains unaffected. slotted anodes. Zinc as the sacrificial anode is the unanimous choice for cathodic protection. He observed that the extent of galvanic protection of the steel and the galvanic corrosion rate of the zinc were functions of the concrete conductivity. Anodes include conductive overlay anodes. overlay thickness. and other factors.3. Zinc may be applied (i) by hot dipping of the rebar in the molten zinc followed by chromatizing treatment to produce galvanized rebars (discussed 339 Unauthenticated | 117. Wyatt /139/ has already detailed the historical developments of various anode systems. it may also cause the formation of macrocells between protected and unprotected steel. The standard electrode potential of the sacrificial anode must be lower than the standard electrode potential of the reinforcement so that during galvanic corrosion. the reinforcement acts as the cathode and remains unattacked. source /140/. the structure to be protected is made into a cathode by supplying an electric current from an external d. and assessment of cathodic protection performance /138/.138 Download Date | 11/20/12 9:22 AM . activated titanium mesh anodes.1. flame or arc sprayed zinc anodes. steel surface area. 4. Zhang /143. He /141/ found that the distributed mesh systems are the latest development and have proved to be very effective. In this method.206. The critical areas of this multi-discipline technology with respect to system performance and future development are the anode system.15. surface conditions. anode overlays. A highly non-uniform current distribution may not only leave some of the reinforcement unprotected. In another paper. This may be present in the form of a coating or separately. conductive coating anodes.

known as sprayed-zinc sacrificial anodes. the concrete and/or any exposed steel reinforcement surface was cleaned thoroughly and roughened.2. improving adhesion of the sprayed metal. The DC current is passed into the electrolyte by means of an internal electrode like a lead-silver alloy or platinum.) ranged from $6/ft 2 to $12/ft2 ($65/m2 to $130/m2) compared to ~$40/ft2 ($370/m2) for conventional impressed-current cathodic protection systems on marine substructures. based upon experience by the Florida Department of Transportation /145/. or weather exposure) was considered a necessary factor for long-term anode performance. This acidic area spreads out from the anodic electrode toward the cathodic area. 16. /147/ for this purpose. 1998 Protection of Steel Reinforcement for Concrete A Review earlier under metallic coating) or (ii) by flame or arc spraying. and the anodic area becomes acidic in nature. 11461 have also found sprayed-zinc coating to be very well applicable to corrosion protection of reinforcement. A number of studies have been directed towards this method /150-157/. McArthur /158/ has shown through modeling that the cathodic area is initially made very alkaline immediately after switch-on. 4. A process has also been developed for catalyzing the Ti coating. Application of zinc in the field was preceded by removing the delaminated concrete and then cleaning the surface of the affected member by sand-blasting. No. Thus. It is found that this alkalinity is produced at the cathodically impressed rebar as the impressed current uses up the dissolved oxygen.149/. This anode is expected to be useful especially where concrete overlays are undesirable and where long life and durability are important /148/. For field installations. It is generally used for rehabilitation work due to its ease of application and low cost. An alloy of zinc like 85Zn-15Al has also been studied by Brousseau et al.206.3. Recently. etc. 340 Unauthenticated | 117. which results in long-term operation at low anodic potentials. because it could maintain cathodic polarization potential of reinforcement and potential decline field during 4 h of depolarization. flame or arc spray techniques /148. Impressed Current Cathodic Protection This system is more flexible but more complex than a galvanic anode system. splash. The basic principle is the same for both systems.15.Vol.138 Download Date | 11/20/12 9:22 AM . except that the impressed current system energizes the anode by means of an external electrical energy source. Periodical water contact (by sea water mist. 4. the typical installed costs (including surface preparation. titanium-based anodes have also been studied which can also be applied to concrete by plasma. Gao et al.

For cathodic protection to work effectively. Preferred electrolytes include water or other solutions. Miller /163/ has developed a process for rehabilitating internally reinforced concrete by electrical treatment. to minimize the release of free chlorine gas into the ambient. 4.138 Download Date | 11/20/12 9:22 AM .c. Voltage is applied between the reinforcement and the distributed electrode. so that it takes part in the cathodic reaction. current similar to cathodic protection of reinforced concrete structures is used to remove chloride ions from concrete. Very often. determining the chloride content in corroding and passive zones and removing the chloride-contaminated concrete. electrolytic material comprised of cellulosic pulp fiber mixed with liquid electrolyte. The anodic area becomes acidic and the alkaline OH" ions are moved away from the rebar as a requirement for continuous current flow.206. /164/ have made a laboratory investigation using activated titanium meshes as anodes and saturated calcium hydroxide or 1M sodium carbonate 341 Unauthenticated | 117. An impressed cathodic d. where the concrete is chloride-contaminated but no corrosion or only slight corrosion of the rebars occurred. Cathodic protection is a permanent installation whereas electrochemical removal is only temporary /162/. Polder et al. such as calcium hydroxide.15. there must be a way for oxygen to difiuse to the cathodic area. Desirably. An anode and an electrolyte are applied to the structure surface and a current is passed between the anode and the reinforcing steel which acts as a cathode.4.Vinod Kumar Corrosion Reviews requires the hydroxyl ions to carry the ionic current. the distributed electrode is formed of a ferrous material reactive with chlorine. Electrochemical Removal of Chloride Ions The conventional technique for repair of old structures consists of locating the corroding areas with the potential mapping technique /159. sound concrete with high compressive strength has to be removed due to excessive chloride contamination. the voltage is discontinued and the adherent electrolyte coating and distributed electrode are removed. electrochemical methods can be used to remove sufficient amounts of chlorides allowing the steel to repassivate.160/. For these cases. Trials are underway to determine if chloride removal by electrokinetics is an effective option /161/. preferably a wire grid to cause migration of chloride ions from the concrete to the electrolyte coating. When the chloride content of the concrete has been reduced to a desired level. It involves applying to surface areas of the concrete a temporary sprayed-on layer of a self-adherent. and produces hydrogen.

Vol.9-3. carbon dioxide and oxygen to the reinforcement Such corrosion finally leads to cracking along the reinforcing bars on account of the expansive nature of the oxidation products.008 in) in width were subject to little CI" penetration in good quality concrete (water-to-cement ratio [w/c] ^ 0. geothite and lepidocrocite make up only 30% of the rust formed within concrete.206. 4. However. The following sections have been devoted to various parameters related to concrete cover which may have an influence on reinforcement corrosion. impermeable concrete. Crack Width Concrete and cement mortar provide excellent corrosion protection to the reinforcement The most cost-effective and efficient means of avoiding corrosion of reinforcement is to provide an adequate cover of dense. chloride can induce corrosion of reinforcement.2. No. Control of Concrete Cover A good-quality. well-placed concrete cover provides the first and most efficient barrier to the aggressive ions and it is believed that it has no substitute in protecting reinforcement from corrosion. the efficiency of chloride removal was much higher when saturated calcium hydroxide electrolyte was used. and the steel will not corrode if this state is maintained /165. /167/ have found that crystalline magnetite. 45% for uncovered bars. Mangat and Guruswamy /169/ showed that cracks under 0.1. when reinforced concrete is subjected to chloride ingress through exposure to de-icing salts and/or marine environments. 16.4) with 342 Unauthenticated | 117. Beeby /168/ has reported that the quality of the concrete and the adequacy of cover over the reinforcing steel was more important than crack size in determining long-term corrosion performance. as compared to approx. The highly alkaline environment within concrete passivates the steel.15. In view of this. 4.138 Download Date | 11/20/12 9:22 AM . They /167/ found through non-linear FEM analysis an equivalent volume expansion ratio of 2. 1998 Protection of Steel Reinforcement for Concrete A Review as electrolyte solution.5. it is appropriate to understand its role towards reinforcement corrosion. Suda et al.5. Based on this it was observed that the loss of only several micrometers of the bar could lead to the formation of longitudinal cracks. They /164/ observed that the proportion of chloride ions removed from the core was a function of the total charge passed and the nature of the external electrolyte.2 mm (0. This can be traced back to a lack of concrete cover over the reinforcement and to the presence of regions of highly permeable concrete which allow rapid transport of chlorides.166/. 4.

80 11. The table shows that a high pH value is obtained for a rich Table 6 pH Values of Various Mix Ratios 7173/ Mix Ratio PH 1 1:2 1 1. The American Concrete Institute (ACI) Building Code calls for low w/c and concrete cover of at least 38 mm (1. which affects the passivation of reinforcement.006 in) in marine environments and 0.18 mm (0. also changes with the mix ratio as given in Table 6. This is due to conversion of free calcium hydroxide to calcium sulphate and hydrated calcium aluminates to more insoluble calcium sulphoaluminates which increases the solid and volume to more than double and causes expansion and disruption of the concrete /173/. 25 mm (0.15 mm (0.Vinod Kumar Corrosion Reviews proper concrete-cover.2. Working Group 3 (CEN/TC104/WG3) are 0.15. while it is as high as 100mm in concrete with high permeability.00 11. The pH value.5 w/c. If the concrete is of high strength and density.4 mm (0. it can effectively protect the reinforcement against corrosion due to lower infiltration.20 12.5:3 1 2:4 1 3:6 14:8 12. The minimum requirements under discussion in Europe by Comitö Europ0en de Normalisation.007 in) where de-icing salts are used /170. adequate selection and control of the mix ratio is veiy important 343 Unauthenticated | 117. It should be noted that the carbonation depth does not exceed 20mm in a dense concrete.70 mix (greater proportion of cement in the concrete mix) and a low pH value for the lean mix This also indicates that there is a steep fall in pH and alkalinity with the decrease in cement content in the mix.016 in) /172/. MixRatio The strength and density of the concrete primarily depend upon the mix ratio (Cement: Sand : Aggregate). The ACI recommended that maximum crack sizes should be 0. 4.5.138 Download Date | 11/20/12 9:22 AM .10 12. Technical Committee 104. It has been observed that 1:4:8 concrete is 100 times more permeable than 1:2:4 concrete /173/.206. It is important to note that the tolerable limit for corrosive ions like chloride and sulphate increases with an increase in the pH value /173/.0984 in) of concrete cover. The actual mix-ratio may vary with duration. and cracks less than 0. In view of the above.171/.5 in).

4.5. No.15. Chloride may also enter into concrete from the external environment to which it is exposed. However. 4. the effect of these variables on the corrosion rate was negligible.3. Newton et al. CT/OK Ratio Chloride ions may enter the concrete. inadvertently.3 decreased mortar and cement paste porosity but did not improve the corrosion performance of embedded steel.206. This may be due to reduced compaction efficiency during placement and lower Ca(OH)2 content in the hardened cement paste /8/. and less drying shrinkage and cracking occur with these mixes. The reaction. This free chloride in the pore solution initiates corrosion in the reinforcement. wind-carried salt spray. 1998 Protection of Steel Reinforcement for Concrete A Review The use of concrete with a minimum cement content with good compaction and w/c (water to cement ratio) < 0. therefore. Gu et al.4 is actively encouraged in structural applications /174/ as it improves strength and reduced permeability is obtained by minimizing paste porosity. however. The proportion of unbound (or free) chloride is. Locke /178/ also found that a chloride ion which diffuses into hardened concrete will initiate corrosion less than that required 344 Unauthenticated | 117. Although codes of building practice specify a maximum chloride content. This chloride does not combine with the hydration products of cement to the same extent as chloride in fresh concrete. through the use of chloride contaminated water for mixing or aggregates /177/ or through calcium chloride used to accelerate hydration and hardening of the cement binder. 16. is never complete and some active soluble chloride remains in equilibrium in the pore fluid.138 Download Date | 11/20/12 9:22 AM . Constantinou et al. the concrete cover and the curing time had a significant effect on the length of time taken to carbonate the specimen. higher and the risk of corrosion is greater. These chloride ions react with the calcium aluminate and aluminoferrite to form insoluble calcium chloroaluminates and calcium chloroferrites in which chloride is bound in non-active forms. 11161 found that the corrosion reactions appeared preferentially to occur on the surface of the rebar embedded in a denser matrix for both the presence and absence of chloride ions. it is difficult to distinguish between free and bound chloride and their effects on steel corrosion /8/. /8/ found that a reduction in w/c from 0. /175/ found that the w/c ratio. such as sea water (tidal and splash zone).Vol. de-icing salts on roads and bridge decks or wetting and drying cycles under a chloride environment.4 to 0. This phenomenon has been explained by the depletion of oxygen concentration at the steel/cement paste interface resulting in the formation of an "anodic area".

206.138 Download Date | 11/20/12 9:22 AM .188 189 w/c is a dominant factor and not the cement content.15. acidsoluble chloride or CL/OH" ratio Neither total chloride content nor CL/OH is a reliable indicator for corrosion risk.179/.6 References 180-182 Remarks >320 183 £4 184 >30 Not a dominant factor 185 186 187. However. The passivation of steel rebar may be disrupted in the presence of chlorides. A universal threshold level is not applicable to different materials and mixes. CI" concentration has a more significant influence on corrosion initiation than CL/OH" 345 Unauthenticated | 117.Vinod Kumar Corrosion Reviews to initiate corrosion with chloride ion mixed in the concrete. a universal threshold level is not applicable to different materials and mixes (Table 7). Table 7 Influence of C170H" Ratio on the Initiation of Corrosion Conditions) Calcium hydroxide solutions simulating real pore fluid in concrete Steel fibers and rebar electrodes embedded in concrete in marine tidal and splash zone environment Steel electrodes "embedded in concrete of different compositions in terms of the Cl'/OH" concentration of their pore fluid Steel electrodes in mortar Reinforcement electrodes embedded in concrete matrices of different cement and water/ cement ratios and exposed to marine environment Influence of pore fluid composition on reinforcement corrosion Rebar electrodes embedded in concrete matrices containing different cement placements and exposed to marine environment Plain concrete Microsilica concrete 13 17-18 cr/off Ratio 0. if a certain Cl'/OH" ratio threshold is exceeded. It has been shown that pitting becomes more likely as the C170H" ratio in the solution is increased /9.

corrosion inhibitors have been developed.4. Andrade et al.15. especially when used in concrete of good quality /193/. /199/ suggested chemical treatment of corroding steel reinforcement through ponding and/or placement of chemically treated mortar after removal of chloride-contaminated concrete. all inhibitors studied did not prevent the physico-chemical interaction of the solution with the metal of the crack-tip. They /196/ found that the greatest effect was provided by NaN0 2 . their use as a curative method. by penetrating the concrete from the outside of an old structure already contaminated. /195/ have studied both methods using Na 2 P0 3 F as inhibitor. Results indicated that Na2P03F may act as an inhibitor of reinforcement corrosion through the hardened concrete.e. Inhibitors In addition to the above protective measures.206. would be of great interest. The common practice is to add them together with the mixing water of concrete. An agent may also be added to the solution to prevent any calcium hydroxide contained in the concrete from precipitating the corrosion inhibitor /198/.Vol. Concrete Additives 4. and only slightly increased the resistance to crack propagatioa The mixture of NaN0 2 with a sodium phosphate derivative and an acyl derivative of tetraamine was found to be very effective for protection from corrosion and corrosion cracking. however. Collins et al. Organic migrating corrosion inhibitors (MIC) have also been developed to protect reinforcement steel /197/. i.1. /196/ have studied the inhibiting effect of NaN0 2 . At the same time. most notably calcium nitrate (Ca(N02>2 /190-193/ which is effective in providing increased corrosion protection.5. 16. Dikkii et al. Na 3 P0 4 and Na 2 Cr0 4 on a 3% solution of NaCl on reinforcement corrosion. Hansen /198/ has suggested drawing the chloride away from the metal and then applying a composition containing ammonium carbamate or ammonium carbonate to the concrete. 1998 Protection of Steel Reinforcement for Concrete A Review 4. /197/ found that MIC provide corrosion protection to rebar in chloride-contaminated concrete without any adverse effect on the structure. Miksic et al. The addition of 1% NaN0 2 increased the resistance to cracking by a factor of 14. 4. Calcium-nitrite based corrosion inhibitor was found to be most effective when applied as a ponding and when placed in backfilled mortar. 346 Unauthenticated | 117. No.4. NaNQ may also be added to prevent pitting on the reinforcement in the amount of about 4% of the concrete /194/.138 Download Date | 11/20/12 9:22 AM .5.

203/. oxygen. Kouloumbi et al. in concrete made with superplasticizers. 5. its mishandling during transportation. The addition of fly ash reduces the corrosion susceptibility of steel in concrete /204-207/. /203/ have found that the use of fly ash was beneficial in immobilizing the chloride ions in non-supeiplasticized concrete. As mentioned above. a barrier must be present to prevent the ingress of harmful ions. bond to steel. Corrosion takes place only when a path exists for the ingress of chloride. However. needs disposal to avoid environmental pollution. however. it is evident that a good concrete cover in terms of quality of ingredients. therefore. bond strength is also reduced due to the smooth surface of epoxy-coated rebars.138 Download Date | 11/20/12 9:22 AM . fabrication.15. a zinc-based sacrificial anode cathodic protection system is considered a better choice than the impressed-current cathodic protection method due to practical difficulties involved with the latter. Epoxy coating is the most popular barrier coating. Zinc coating initially acts as a barrier and subsequently provided sacrificial cathodic protection. Kayyali et al. In view of this. CONCLUDING REMARKS From the above discussion. This causes corrosion of reinforcement leading to premature failure. FlyAsh Fly ash is a waste material and. in the concrete cover.5. and feasibility of application Steel reinforcement can also be prevented through cathodic protection.2.. This barrier may be in the form of a coating on the reinforcement or on the surface of the concrete cover. In view of this. has no substitute for the prevention of reinforcement corrosion. storage.Vinod Kumar Corrosion Reviews 4. mix proportion.206. Other coating systems are either on a laboratory scale or have found limited application. etc. This situation is unavoidable in practice and the above path exists. etc.4. resistance to damage by rough handling. placement and construction may cause a serious corrosion problems due to localized attack Apart from this. The important criteria for selection of any coating are: its resistance to chemical attack. sulphur dioxide. These include 347 Unauthenticated | 117. /206/ found that use of a 30% fly ash mix provided the most effective protection. water-cement ratio. work has been carried out to study the addition of fly ash in partial substitution of Portland cement in concrete on concrete porosity and resistivity /200-202/ as well as on reinforcement corrosion /202. Galvanized rebars are also popular. the inclusion of fly ash was found to cause a greater release of chloride ions into the pore solution..

K. Jr.J.^C/SP-109. Novokshchenov.198 (1970). 153. 775-779 (1972). Phang. Materials and Structures. T.S. SAEST. C.S.138 Download Date | 11/20/12 9:22 AM .109-114 (1982). 348 Unauthenticated | 117. Concrete: Structure. Diamond. Br. Proc. Con. NACE. Corros.L. 16. 3.. nature of environment and cost of application 7. Trans. 1998 Protection of Steel Reinforcement for Concrete A Review non-uniform distribution of current due to the complex non-homogeneous nature of concrete. Englewood Cliffs.J.20-29. 11. I. O. 279 (1981).206. 4.. 26 (1986). J.J. 6. 35(5-8). V. 9. life expectancy.C. 1649-1660 (1993). Br. J. 22. In summary. C. No. Solomon. it can be concluded that the utmost care should be taken dining concrete-mix preparation and construction The choice of other protection methods will depend upon the type of structure to be protected. efforts have been made to develop reinforcement steel with better corrosion resistance. Gouda.E. R.15. P. 13..L.K. placement or even construction. W. Properties and Materials. C. Mater. 5. Corros. 101-107 (1988). design changes. Mishawa. 31-45 (1991). etc. 7. El Busaidy.Vol. electrical connections to all embedded rebars. NJ. Cook and W. 2. Mishra. they do not require any skilled labour and capital investment. 11.K. P.. Newton and J. fabrication. 23 (2-3). Corrosion Science. Bhasin. 4. O. Κ.W. Uonoto and S. In recent years. 392-400 (1995). 12. 39. ASTM STP 629. 26(1). Gjorv. TX. Page and K. Perform. Vennesland and A. large capital investment. and suitable provision in the structural design A large number of studies are also directed towards concrete additives like corrosion inhibitor and fly ash which have been found useful in preventing reinforcement corrosion. storage. Page and P. REFERENCES 1.H. Lambert. Res.127-146 (1988). "Chloride Corrosion of Steel in Concrete". 5. 942 (1987). Cem. Nature. H. Prentice Hall. 8. and S. 1986. Shimodaira. J.M Stykes. Barneyback. Sei. 28 (181).. Treadway. McCoy. Hashimoto. These corrosion resistant rebars do not require any special care during transportation. 10. Τ. Bird and B. Houston. M F . Mehta. V. of the 5th International Congress on Metallic Corrosion. 297. Moreover. Suetaka and S. Mater.

D. Keiser. Watkins. Ellis Horwood. H. 17. Vennesland. Page. 29.M. P. 297. 14 (1995). Philadelphia. D. 23. Hegedus. Miyagawa. 32. 14-17 (1995). 25. El Tarras.J.. Vennesland. London. 37. 229 (1979). Cem. J.E.L.. 1983. J. Arganis. 34. 26.J. Fukinbara. C. Μ Shimizu and Y. J. 9. G. 395 (1981).). Soc. Institute of Chemical Engineers. 38.15. J. Page.. Con. 76. 1987.. 18. Francies and T. 912.). A. 1984.. 16. 1960. Cem. TX 77128 (1994). Rugby. 19. Comm. O. Corros. Kobe 349 Unauthenticated | 117. Kawakami. pp. T.J. 453 (1982). 9. Carpio and C.R Büenfeld and J. Corrosion. 255. Constr. 30. Page and K. Paper 3. Corrosion. Lambert. in: Corrosion in Simulated Environments. 1985. Corrosion Science. in: Corrosion of Reinforcement in Concrete Construction. Chichester. N. ASTM. 517 (1986). Lea and C. Materials Performance.197 (1979).21 (1982). Con. Newman. Cem. 23. Andrade. 34(6). 16.S. 27. alKhalaf and C. 36. N. 33. Res. NACE Int. 15. Hernandez. Mater. in press. Corrosion. Res. C. Con. in: The Chemistry and Chemically Related Properties of Cement.J. P. F.W. Br. 21. Martinez. Wang and I. C. pp. Con Res. Govt. Paper No.F. Page. ISU.L. N. STP 970.. 251-259(1983).1449-1457 (1990). 24. W. M. Br. 1. 875-884 (1991). 50(6).R Büenfeld..E.M. 17.L. Hernandez. 35. Con. Newman and C. Wilkins and P. 91 (1983).109 (1982). Series 87. Crane (ed.. Cem. Nagain. 28. Martinez. J. Pereia and L. Proc. Res. "The Durability of Reinforced Concrete in Sea-Water". Res. Houston.O. Iwasaki. 477-485 (1994). L. PA.Vinod Kumar Corrosion Reviews 14. Ceram.R Short and A. F. J.J. Page and O. 119.L. 20. Mag. 427.N. Arganis. A.M.L. Marine Sei.. P. 11. Research Announcements and Index. Gonzalez and C. pp. Brown and R Heidersbach.P. 36. Corrosion Prevention & Control. J. N. V. Nature. 22.L. O. Treadway. 17. C. Vinod Kumar. Page and N.R Short. L. Lawrence. C. Box 218340. Glaser (ed. Lee (eds.206. Gjorv. Chem Ε Symp. Silverman. P. 35. 47(11).M Sykes.. Balkwill and J.67 (1984).B.C.E. Darwin. H. 31. C. Gjorv and O. I.). pp. Novokschchenov.138 Download Date | 11/20/12 9:22 AM .198 (1970). Caipio and C. HMSO. "Diffusion and Reaction of Chloride Ions in Porous Concrete".H.B. G.P.

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