Chloride-induced corrosion of steel rebars in simulated pore solutions of alkali-activated concretes

Abstract The passivation and chloride-induced depassivation of steel rebars immersed in varying alkaline environments (0.80 M, 1.12 M and 1.36 M NaOH solutions), simulating the pore solutions of low-Ca alkali-activated concretes, were investigated using a range of electrochemical techniques. The passive film on the steel rebars was complex in chemical makeup, composed of Fe–hydroxides, oxy-hydroxides and oxides. An increased degree of passivation of the rebars was observed when exposed to solutions with higher hydroxide concentrations. The critical chloride level ([Cl−]/[OH−] ratio) required to induce depassivation of steel was strongly dependent on the alkalinity of the pore solution, and was found to be 0.90, 1.70 and 2.40 for 0.80 M, 1.12 M and 1.36 M NaOH solutions, respectively. These values all correspond to a constant value of [Cl−]/[OH−]3 = 1.25, which is a novel relationship to predict the onset of pitting, interlinking chloride concentration and the solubility of the passive film.

[1]  G. A. McRae,et al.  The effect of concrete pore solution composition on the quality of passive oxide films on black steel reinforcement , 2009 .

[2]  H. Strehblow,et al.  Corrosion, layer formation, and oxide reduction of passive iron in alkaline solution: a combined electrochemical and surface analytical study , 1987 .

[3]  D. Hausmann,et al.  STEEL CORROSION IN CONCRETE -- HOW DOES IT OCCUR? , 1967 .

[4]  John L. Provis,et al.  Pore solution composition and alkali diffusion in inorganic polymer cement , 2010 .

[5]  Carmen Andrade,et al.  Corrosion rate monitoring in the laboratory and on-site , 1996 .

[6]  V. K. Gouda,et al.  Corrosion and Corrosion Inhibition of Reinforcing Steel: II. Embedded In Concrete , 1970 .

[7]  Anders Rønnquist,et al.  Probabilistic considerations on the effect of specimen size on the critical chloride content in reinforced concrete , 2011 .

[8]  M. Pourbaix Thermodynamics and corrosion , 1990 .

[9]  Stefania Manzi,et al.  Corrosion behavior of steel in alkali-activated fly ash mortars in the light of their microstructural, mechanical and chemical characterization , 2016 .

[10]  Rupert J. Myers,et al.  A thermodynamic model for C-(N-)A-S-H gel: CNASH_ss. Derivation and validation , 2014 .

[11]  O. A. Kayyali,et al.  THE C1-/OH- RATIO IN CHLORIDE-CONTAMINATED CONCRETE - A MOST IMPORTANT CRITERION , 1995 .

[12]  Arnaud Castel,et al.  Chloride-induced corrosion of reinforcement in low-calcium fly ash-based geopolymer concrete , 2016 .

[13]  Alberto A. Sagüés,et al.  Chloride Corrosion Threshold of Reinforcing Steel in Alkaline Solutions—Open-Circuit Immersion Tests , 2001 .

[14]  V. Gouda Corrosion and Corrosion Inhibition of Reinforcing Steel: I. Immersed in Alkaline Solutions , 1970 .

[15]  J. R. Vilche,et al.  The voltammetric detection of intermediate electrochemical processes related to iron in alkaline aqueous solutions , 1981 .

[16]  A. Frumkin,et al.  Kinetics of electrode processes on the iron electrode , 1947 .

[17]  K. K. Sagoe-Crentsil,et al.  Steel in concrete: Part II Electron microscopy analysis , 1989 .

[18]  J. Provis Geopolymers and other alkali activated materials: why, how, and what? , 2014 .

[19]  C. K. Larsen,et al.  Chloride induced reinforcement corrosion : Rate limiting step of early pitting corrosion , 2011 .

[20]  G. Duffó,et al.  Corrosion of reinforcing steel in simulated concrete pore solutions: Effect of carbonation and chloride content , 2004 .

[21]  Stefano P. Trasatti,et al.  Electrochemical characterization of mild steel in alkaline solutions simulating concrete environment , 2015 .

[22]  G. Glass,et al.  The inhibitive effects of electrochemical treatment applied to steel in concrete , 2000 .

[23]  C. Andrade,et al.  Synthetic concrete pore solution chemistry and rebar corrosion rate in the presence of chlorides , 1990 .

[24]  J. R. Brown,et al.  XPS depth profiling study on the passive oxide film of carbon steel in saturated calcium hydroxide solution and the effect of chloride on the film properties , 2011 .

[25]  Carolyn M. Hansson,et al.  Reinforcing steel passivation in mortar and pore solution , 2007 .

[26]  Digby D. Macdonald,et al.  A Point Defect Model for Anodic Passive Films II . Chemical Breakdown and Pit Initiation , 1981 .

[27]  L. Burke,et al.  The formation and stability of hydrous oxide films on iron under potential cycling conditions in aqueous solution at high pH , 1986 .

[28]  Karin Pettersson,et al.  Corrosion threshold value and corrosion rate in reinforced concrete , 1992 .

[29]  M. Jayalakshmi,et al.  Passivation and Hydrogen Evolution Studies on Iron in Alkali Solutions , 1994 .

[30]  Marcel Pourbaix,et al.  Applications of electrochemistry in corrosion science and in practice , 1974 .

[31]  W. Kenan,et al.  Impedance Spectroscopy: Emphasizing Solid Materials and Systems , 1987 .

[32]  R. Snellings,et al.  The pore solution of blended cements: a review , 2016 .

[33]  H. Neugebauer,et al.  In Situ FTIR Spectroscopy of Iron Electrodes in Alkaline Solutions II . External Reflection Absorption Spectroscopy , 1990 .

[34]  D. Macdonald,et al.  The cyclic voltammetry of carbon steel in concentrated sodium hydroxide solution , 1978 .

[35]  J. M. Bastidas,et al.  Corrosion behaviour of a new low-nickel stainless steel embedded in activated fly ash mortars , 2011 .

[36]  David A. Harrington,et al.  Mechanism and equivalent circuits in electrochemical impedance spectroscopy , 2011 .

[37]  X. Nóvoa,et al.  Study of passive films formed on mild steel in alkaline media by the application of anodic potentials , 2009 .

[38]  Sebastián Feliu,et al.  Initial steps of corrosion in the steel/Ca(OH)2 + Cl− system: The role of heterogeneities on the steel surface and oxygen supply , 1993 .

[39]  C. M. Rangel,et al.  Use of EIS, ring-disk electrode, EQCM and Raman spectroscopy to study the film of oxides formed on iron in 1 M NaOH , 2002 .

[40]  P. A. Brook,et al.  The breakdown of passive films on iron , 1988 .

[41]  G. Glass,et al.  The presentation of the chloride threshold level for corrosion of steel in concrete , 1997 .

[42]  Ueli Angst,et al.  Critical Chloride Content in Reinforced Concrete: A Review , 2009 .

[43]  Petrus Christiaan Pistorius,et al.  The nucleation and growth of corrosion pits on stainless steel , 1993 .

[44]  Ángel Palomo,et al.  Corrosion resistance in activated fly ash mortars , 2005 .

[45]  J. R. Vilche,et al.  The potentiodynamic behaviour of iron in alkaline solutions , 1979 .

[46]  Nick R. Buenfeld,et al.  The participation of bound chloride in passive film breakdown on steel in concrete , 2000 .

[47]  S. Bernal,et al.  Geopolymers and Related Alkali-Activated Materials , 2014 .

[48]  P. Duxson,et al.  Effect of Alkali Cations on Aluminum Incorporation in Geopolymeric Gels , 2005 .

[49]  John O’M. Bockris,et al.  Surface Electrochemistry: A Molecular Level Approach , 1993 .

[50]  Cruz Alonso,et al.  Electrochemical impedance spectroscopy for studying passive layers on steel rebars immersed in alkaline solutions simulating concrete pores , 2007 .

[51]  A. Fernández-Jiménez,et al.  A study on the passive state stability of steel embedded in activated fly ash mortars , 2008 .

[52]  Brian B. Hope,et al.  The influence of surface finish of reinforcing steel and ph of the test solution on the chloride threshold concentration for corrosion initiation in synthetic pore solutions , 1996 .

[53]  D. Macdonald,et al.  The Electrochemistry of Iron in lM Lithium Hydroxide Solution at 22° and 200°C , 1973 .

[54]  Marcel Pourbaix,et al.  Lectures on Electrochemical Corrosion , 1973 .

[55]  H. Neugebauer,et al.  The in situ determination of oxidation products on iron electrodes in alkaline electrolytes using multiple internal reflection fourier transform infrared spectroscopy , 1981 .

[56]  G. A. McRae,et al.  Electrochemical investigation of chloride-induced depassivation of black steel rebar under simulated service conditions , 2010 .

[57]  Ueli Angst,et al.  Chloride induced reinforcement corrosion: Electrochemical monitoring of initiation stage and chloride threshold values , 2011 .

[58]  J. Pan,et al.  Localized corrosion behaviour of reinforcement steel in simulated concrete pore solution , 2009 .

[59]  A. Diab,et al.  Environmental factors affecting the corrosion behavior of reinforcing steel. IV. Variation in the pitting corrosion current in relation to the concentration of the aggressive and the inhibitive anions , 2010 .

[60]  O. Burkan Isgor,et al.  The effect of simulated concrete pore solution composition and chlorides on the electronic properties of passive films on carbon steel rebar , 2016 .

[61]  John L. Provis,et al.  Chemical Research and Climate Change as Drivers in the Commercial Adoption of Alkali Activated Materials , 2010 .

[62]  R. Newman,et al.  Localised dissolution kinetics, salt films and pitting potentials , 1997 .