Skip to main content
SpringerLink
Log in

The Onset of Chloride-Induced Corrosion in Reinforced Cement-Based Materials as Verified by Embeddable Chloride Sensors

  • Chapter
  • First Online:
Concrete Durability

Abstract

The need for an accurate determination of the chloride threshold value for corrosion initiation in reinforced concrete has long been recognized. Numerous investigations and reports on this subject are available. However, the obtained chloride threshold values have always been, and still are, debatable. The main concern is linked to the methods for corrosion detection and chloride content determination in view of the critical chloride content itself. In order to measure the chloride content, relevant to the corrosion initiation on steel, destructive methods are used. These traditional methods are inaccurate, expensive, time consuming and noncontinuous. Therefore, the application of a cost-effective Ag/AgCl ion selective electrode (chloride sensor) to measure the chloride content directly and continuously is desirable. The advantage would be an in situ measurement, in depth of the concrete bulk, as well as at the steel/concrete interface.

The aim of this work was to evaluate the importance of the sensor’s properties for a reliable chloride content measurement. The main point of interest with this regard was the contribution of the AgCl layer and Ag/AgCl interface within the process of chloride content determination in cementitious materials. The electrochemical behavior of sensors and steel, both embedded in cement paste in a close proximity, hence in identical environment, were recorded and outcomes correlated towards clarifying the objectives of this work. The main point of interest was to simultaneously detect and correlate the time to corrosion initiation and the critical chloride content.

The electrochemical response of steel was monitored to determine the onset of corrosion activity, whereas the sensors’ electrochemical response accounted for the chloride content. For evaluating the electrochemical state of both sensors and steel, electrochemical impedance spectroscopy (EIS) and open circuit potential (OCP) measurements were employed. The results confirm that determination of the time to corrosion initiation is not always possible and straightforward through the application of OCP tests only. In contrast, EIS is a nondestructive and reliable method for determination of corrosion activity over time. The obtained results for corrosion current densities for the embedded steel, determined by EIS, were in a good agreement with the sensors’ half-cell potential readings. In other words, the sensors are able to accurately determine the chloride ions activity at the steel/cement paste interface, which in turn brings about detectable by EIS changes in the active/passive state of steel.

The electrochemical response was supported by studies on the morphology and surface chemistry of the sensors, derived from electron microscopy (ESEM) and X-ray photoelectron spectroscopy (XPS). It can be concluded that the accuracy of the sensors, within detection of the time to corrosion initiation and critical chloride content, is determined by the sensors’ properties in terms of thickness and morphology of the AgCl layer, being an integral part of the Ag/AgCl sensors.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 79.99
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 99.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 139.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  1. Mehta PK, Monteiro PJM (2006) Concrete: microstructure, properties, and materials. McGraw-Hill, New York

    Google Scholar 

  2. Bertolini L, Elsener B, Pedeferri P, Polder R (2004) Corrosion of steel in concrete. Weinheim, Wiley VCH

    Google Scholar 

  3. Silva N (2013) Chloride induced corrosion of reinforcement steel in concrete – threshold values and ion distributions at the concrete-steel interface. Dissertation in Civil Engineering (PhD thesis), Goteborg, Chalmers University of Technology

    Google Scholar 

  4. Angst U, Vennesland O (2007) Critical chloride content. State of the art- SINTEF RE-PORT

    Google Scholar 

  5. Angst U, Elsener B, Larsen CK, Vennesland O (2009) Critical chloride content in reinforced concrete – a review. Cem Concr Res 39(12):1122–1138

    Article  Google Scholar 

  6. Andrade C, Keddam M, Novoa XR, Perez MC, Rangel CM, Takenouti H (2001) Electrochemical behaviour of steel rebars in concrete: influence of environmental factors and cement chemistry. Electrochim Acta 46(24–25):3905–3912

    Article  Google Scholar 

  7. Song HW, Saraswathy V (2007) Corrosion monitoring of reinforced concrete structures-a review. Int J Electrochem Sci 2:1–28

    Google Scholar 

  8. Andradel C, Soler L, Novoa XR (1995) Advances in electrochemical impedance measurements in reinforced concrete. Mater Sci Forum 192–194:843–856

    Article  Google Scholar 

  9. Koleva DA (2007) Pulse cathodic protection, an improved cost-effective alternative. PhD thesis, Delft University Press, Delft

    Google Scholar 

  10. Poulsen S, Sorensen HE (2012) Chloride threshold value- state of the art. Danish Expert Centre for Infrastructure Constructions

    Google Scholar 

  11. Montemor MF, Simoes AMP, Ferreira MGS (2003) Chloride-induced corrosion on reinforcing steel: from the fundamentals to the monitoring techniques. Cem Concr Compos 25(4–5):491

    Article  Google Scholar 

  12. Angst U, Vennesland O, Myrdal R (2009) Diffusion potentials as source of error in electrochemical measurements in concrete. Mater Struct 42(3):365–375

    Article  Google Scholar 

  13. Elsener B, Zimmermann L, Bohni H (2003) Non-destructive determination of the free chloride content in cement based materials. Mater Corros 54(6):440–446

    Article  Google Scholar 

  14. Molina M (1993) Zerstörungsfreie Erfassung der gelösten Chloride im Beton. Diss. ETH, Nr. 10315, ETH Zurich

    Google Scholar 

  15. Atkins CP, Scantlebury JD, Nedwell PJ, Blatch SP (1996) Monitoring chloride concentrations in hardened cement pastes using ion selective electrodes. Cem Concr Res 26(2):319–324

    Article  Google Scholar 

  16. Atkins CP, Carter MA, Scantlebury JD (2001) Sources of error in using silver/silver chloride electrodes to monitor chloride activity in concrete. Cem Concr Res 31(8):1207–1211

    Article  Google Scholar 

  17. Angst U, Elsener B, Larsen CK, Vennesland O (2010) Potentiometric determination of the chloride ion activity in cement based materials. J Appl Electrochem 40(3):561–573

    Article  Google Scholar 

  18. Angst UM, Polder R (2014) Spatial variability of chloride in concrete within homogeneously exposed areas. Cem Concr Res 56:40–51

    Article  Google Scholar 

  19. Moody GJ, Rigdon LP, Meisenheimer RG, Frazer JW (1981) Selectivity parameters of homogeneous solid –state chloride ion-selective electrodes and the surface, morphology of silver chloride – silver sulphide discs under simulated interference conditions. Analyst 106(1262):547–556

    Article  Google Scholar 

  20. Duffo GS, Farina SB, Giordano CM (2009) Characterization of solid embeddable reference electrodes for corrosion monitoring in reinforced concrete structures. Electrochim Acta 54(3):1010–1020

    Article  Google Scholar 

  21. Pargar F, Koleva DA, Koenders EAB, van Breugel K (2014) Nondestructive de-termination of chloride ion using Ag/AgCl electrode prepared by electrochemical anodization. In: 13th international conference on durability of building materials and components (DBMC 2014), Sao Paulo

    Google Scholar 

  22. Polk BJ, Stelzenmuller A, Mijares G, MacCrehan W, Gaitan M (2006) Ag/AgCl microelectrodes with improved stability for microfluidics. Sensors Actuators 114(1):239–247

    Article  Google Scholar 

  23. Shirley DA (1972) High-resolution X-ray photoemission spectrum of the valence bands of gold. Phys Rev B 5(12):4709–4714

    Article  Google Scholar 

  24. Scofield JH (1976) Hartree-slater subshell photoionization cross-sections at 1254 and 1487 eV. J Electron Spectrosc Relat Phenom 8(2):129–137

    Article  Google Scholar 

  25. Jin X, Lu J, Liu P, Tong H (2003) The electrochemical formation and reduction of a thick AgCl deposition layer on a silver substrate. J Electroanal Chem 542:85–96

    Article  Google Scholar 

  26. Bozzini B, Giovannelli G, Mele C (2007) Electrochemical dynamics and structure of the Ag/AgCl interface in chloride-containing aqueous solutions. Surf Coat Technol 201(8):4619–4627

    Article  Google Scholar 

  27. Ha H, Payer J (2011) The effect of silver chloride formation on the kinetics of silver dissolution in chloride solution. Electrochim Acta 56(7):2781–2791

    Article  Google Scholar 

  28. Lal H, Thirsk HR, Wynne-Jones WFK (1951) A study of the behaviour of polarized electrodes. Part I. The silver/silver halide system. Trans Faraday Soc 47:70–77

    Article  Google Scholar 

  29. Fischer T (2009) Materials science for engineering students. Elsevier, San Diego

    Google Scholar 

  30. ASTM C 876 (1991) Standard test method for half-cell potentials of uncoated reinforcing steel in concrete

    Google Scholar 

  31. Angst UM, Elsener B, Larsen CK, Vennesland O (2011) Chloride induced reinforcement corrosion: electrochemical monitoring of initiation stage and chloride threshold values. Corros Sci 53(4):1451–1464

    Article  Google Scholar 

  32. Page CL, Treadaway KWJ (1982) Aspects of the electrochemistry of steel in concrete. Nature 297:109–115

    Article  Google Scholar 

  33. Bertolini L, Redaelli E (2009) Depassivation of steel reinforcement in case of pitting corrosion: detection techniques for laboratory studies. Mater Corros 60(8):608–616

    Article  Google Scholar 

  34. Elsener B (2001) Half-cell potential mapping to assess repair work on RC structures. Constr Build Mater 15(2–3):133–139

    Article  Google Scholar 

  35. Elsener B (2002) Macrocell corrosion of steel in concrete – implications for corrosion monitoring. Cem Concr Compos 24(1):65–72

    Article  Google Scholar 

  36. Elsener B, Andrade C, Gulikers J, Polder R, Raupach M (2003) Half-cell potential measurements – potential mapping on reinforced concrete structures, RILEM TC 154-EMC: electrochemical techniques for measuring metallic corrosion, recommendations. Mater Struct 36:461–471

    Article  Google Scholar 

  37. Bohni H (2005) Corrosion in reinforced concrete structures. CRC, New York

    Book  Google Scholar 

  38. Davis JR (2000) Corrosion: understanding the basics. ASM International, Materials Park

    Google Scholar 

  39. Svegl F, Kalcher K, Grosse-Eschedor YJ, Balonis M, Bobrowski A (2006) Detection of chlorides in pore water of cement based materials by potentiometric sensors. J Rare Metal Mater Eng 35(3):232–237

    Google Scholar 

  40. Climent-Llorca MA, Viqueira-Perez E, Lopez-Atalaya MM (1996) Embeddable Ag/AgCl sensors for in situ monitoring chloride contents in concrete. Cem Concr Res 26:1157–1161

    Article  Google Scholar 

  41. Austin LG, Lerner H (1965) Review of fundamental investigations of silver oxide electrodes. Pennsylvania State University, University Park

    Google Scholar 

  42. Angst U, Vennesland O (2009) Detecting critical chloride content in concrete using embedded ion selective electrodes–effect of liquid junction and membrane potentials. Mater Corros 60(8):638–643

    Article  Google Scholar 

  43. Ford SJ, Shane JD, Mason TO (1998) Assignment of features in impedance spectra of the cement-paste/steel system. Cem Concr Res 28(12):1737–1751

    Article  Google Scholar 

  44. Poupard O, Ait-Mokhtar A, Dumargue P (2004) Corrosion by chlorides in reinforced concrete: determination of chloride concentration threshold by impedance spectroscopy. Cem Concr Res 34(6):991–1000

    Article  Google Scholar 

  45. Trabanelli G, Monticelli C, Grassi V, Frignani A (2005) Electrochemical study on inhibitors of rebar corrosion in carbonated concrete. Cem Concr Res 35(9):1804–1813

    Article  Google Scholar 

  46. Subramaniam KV, Bi M (2009) Investigation of the local response of the steel–concrete interface for corrosion measurement. Corros Sci 51(9):1976–1984

    Article  Google Scholar 

  47. Riberto DV, Souza CAC, Abrantes JCC (2015) Use of electrochemical impedance spectroscopy (EIS) to monitoring the corrosion of reinforced concrete. IBRACON Struct Mater J 8(4):529–546

    Article  Google Scholar 

  48. Serdar M, Meral C, Kunz M, Bjegovic D, Wenk HR, Monteiro PJM (2015) Spatial distribution of crystalline corrosion products formed during corrosion of stainless steel in concrete. Cem Concr Res 71:93–105

    Article  Google Scholar 

  49. Tang F, Chen G, Brow RK (2016) Chloride-induced corrosion mechanism and rate of enamel- and epoxy-coated deformed steel bars embedded in mortar. Cem Concr Res 82:58–73

    Article  Google Scholar 

  50. Andrade C, Gonzalez JA (1978) Quantitative measurements of corrosion rate of reinforcing steels embedded in concrete using polarization resistance measurements. Mater Corros 29(8):515–519

    Article  Google Scholar 

  51. Thompson NG, Lawson KM (1991) An electrochemical method for detecting ongoing corrosion of steel in a concrete structure with CP applied. Strategic Highway Research Program, National Research Council, Washington, DC

    Google Scholar 

  52. Feliu V, Gonzalez JA, Andrade C, Feliu S (1998) Equivalent circuit for modelling the steel-concrete interface. I. Experimental Evidence and theoretical predictions. Corros Sci 40(6):975–993

    Article  Google Scholar 

  53. Andrade C, Soler L, Alonso C, Novoa XR (1995) Importance of geometrical considerations in the measurement of corrosion by means of A.C. impedance. Corros Sci 37(12):2013–2023

    Article  Google Scholar 

  54. Gu P, Beaudoin JJ (1998) Estimation of steel corrosion rate in reinforced concrete by means of equivalent circuit fittings of impedance spectra. Adv Cem Res 10(2):43–56

    Article  Google Scholar 

  55. Koleva DA, Boshkov N, van Breugel K, de Wit JHW (2011) Steel corrosion resistance in model solutions, containing waste materials. Electrochim Acta 58(30):628–646

    Article  Google Scholar 

  56. Joiret S, Keddam M, Novoa XRN, Perez MCP, Rangel C, Takenouti H (2002) Use of EIS, ring-disk electrode, EQCM and Raman spectroscopy to study the film of oxides formed on iron in 1M NaOH. Cem Concr Compos 24(1):7–15

    Article  Google Scholar 

  57. Abreu CM, Cristobal MJ, Losada R, Novoa XR, Pena G, Perez MC (2006) Long-term behaviour of AISI 304L passive layer in chloride containing medium. Electrochim Acta 51(8–9):1881–1890

    Article  Google Scholar 

  58. Andrade C, Blanco VM, Collazo A, Keddam M, Novoa XR, Takenouti H (1999) Cement paste hardening process studied by impedance spectroscopy. Electrochim Acta 44(24):4313–4318

    Article  Google Scholar 

  59. Wei J, Fu XX, Dong JH, Ke W (2012) Corrosion evolution of reinforcing steel in concrete under dry/wet cyclic conditions contaminated with chloride. J Mater Sci Technol 28(10):905–912

    Article  Google Scholar 

  60. Morozov Y, Castela AS, Dias APS, Montemor MF (2013) Chloride-induced corrosion behavior of reinforcing steel in spent fluid cracking catalyst modified mortars. Cem Concr Res 47(4):1–7

    Article  Google Scholar 

  61. Duarte RG, Castela AS, Neves R, Freirea L, Montemor MF (2014) Corrosion behavior of stainless steel rebars embedded in concrete: an electrochemical impedance spectroscopy study. Electrochim Acta 124:218–224

    Article  Google Scholar 

  62. Zhao B, Li JH, Hu R-G, Du RG, Lin CJ (2007) Study on the corrosion behavior of reinforcing steel in cement mortar by electrochemical noise measurements. Electrochim Acta 52(12):3976–3984

    Article  Google Scholar 

  63. Jamil HE, Montemor MF, Boulif R, Shriri A, Ferreira MGS (2004) An electrochemical and analytical approach to the inhibition mechanism of an amino-alcohol-based corrosion inhibitor for reinforced concrete. Electrochim Acta 49(5):836

    Article  Google Scholar 

  64. Zheng H, Li W, Ma F, Kong Q (2014) The performance of a surface-applied corrosion inhibitor for the carbon steel in saturated Ca(OH)2 solutions. Cem Concr Res 55:102–108

    Article  Google Scholar 

  65. Castellote M, Andrade C, Alonso C (2002) Accelerated simultaneous determination of the chloride depassivation threshold and of the non-stationary diffusion coefficient values. Corros Sci 44(11):2409–2424

    Article  Google Scholar 

  66. McCarthy MJ, Giannakou A, Jones MR (2004) Comparative performance of chloride attenuating and corrosion inhibiting systems for reinforced concrete. Mater Struct 37(10):671–679

    Article  Google Scholar 

  67. Montes P, Bremner TW, Lister DH (2004) Influence of calcium nitrite inhibitor and crack width on corrosion of steel in high performance concrete subjected to a simulated marine environment. Cem Concr Compos 26:243–253

    Article  Google Scholar 

  68. Cusson D, Qian S, Chagnon N, Baldock B (2008) Corrosion-inhibiting systems for durable concrete bridges. I: five-year field performance evaluation. J Mater Civil Eng 20(20):20–28

    Article  Google Scholar 

  69. COST 52 (2002) Final report, Corrosion of steel in reinforced concrete structures, Luxembourg

    Google Scholar 

  70. Li L, Sague AA (2001) Chloride corrosion threshold of reinforcing steel in alkaline solutions- open-circuit immersion tests. Corrosion 57(1):19–28

    Article  Google Scholar 

  71. Gouda VK (1970) Corrosion and corrosion inhibition of reinforcing steel: I. Immersed in alkaline solutions. Br Corros J 5(5):198–203

    Article  Google Scholar 

  72. Moreno M, Morris W, Alvarez MG, Duffo GS (2004) Corrosion of reinforcing steel in simulated concrete pore solutions: effect of carbonation and chloride content. Corros Sci 46(11):2681–2699

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Faculty of Civil Engineering and Geosciences, Department Materials and Environment, Delft University of Technology, Stevinweg 1, 2628, CN, Delft, The Netherlands

    F. Pargar & Klaas van Breugel

  2. Faculty of Civil Engineering and Geosciences, Section Materials and Environment, Delft University of Technology, Stevinweg 1, 2628, CN, Delft, The Netherlands

    Dessi A. Koleva

  3. Institute of Catalysis, Bulgarian Academy of Sciences, Acad. G. Bonchev str., bl. 11, 1113, Sofia, Bulgaria

    H. Kolev

Authors
  1. F. Pargar
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dessi A. Koleva
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. H. Kolev
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Klaas van Breugel
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to F. Pargar .

Editor information

Editors and Affiliations

  1. Universidad Internacional (UNINTER), Cuernavaca, Morelos, Mexico

    Luis Emilio Rendon Diaz Miron

  2. Faculty of Civil Engineering and Geosciences, Section Materials and Environment, Delft University of Technology, Delft, Zuid-Holland, The Netherlands

    Dessi A. Koleva

Rights and permissions

Reprints and permissions

Copyright information

© 2017 Springer International Publishing AG

About this chapter

Cite this chapter

Pargar, F., Koleva, D.A., Kolev, H., van Breugel, K. (2017). The Onset of Chloride-Induced Corrosion in Reinforced Cement-Based Materials as Verified by Embeddable Chloride Sensors. In: Rendon Diaz Miron, L., Koleva, D. (eds) Concrete Durability. Springer, Cham. https://doi.org/10.1007/978-3-319-55463-1_3

Download citation

Publish with us

Policies and ethics

Search

Navigation