Lecture 1

Repair and Maintenance of Concrete Structures

Corrosion of embedded metal
Embedded Metal Corrosion
(Significance and fundamentals of corrosion)

ELECTROLYTE

METAL

Radhakrishna G. Pillai
Department of Civil Engineering
Indian Institute of Technology Madras, Chennai, India

NPTEL – MOOC Course on Maintenance and Repair of Concrete Structures

Courtesy: Some images are sourced from the internet for demonstration purposes.
Outline of
Module on Embedded Metal Corrosion

• Significance
• Fundamentals of corrosion
• Carbonation-induced corrosion
• Chloride-induced corrosion
• Different types of steel reinforcement and
precautions to be taken
• Corrosion in prestressed concrete
Sunshine Skyway bridge, Florida

• In 1980 this bridge was hit by a cargo ship and a 1200-ft section of
bridge fell into the Tampa Bay.
• Replaced with a segmental, post-tensioned (PT) bridge in 1987.
• Only 13 years later,
– PT tendon of the new bridge failed.
• Case study - if two tendons fail,
– PT bridge can collapse (Pillai 2009).

• https://www.tampabay.com/resizer/bRh2m43Q1mwAMKB0N9uh5Rh9pGk=/1370x0/smart/filters:quality(60)/arc-anglerfish-arc2-prod-
tbt.s3.amazonaws.com/public/MJX74QLL5VDCHE63H3MSTIPFAU.JPG
• https://study.com/cimages/multimages/16/sunsky.jpg
• https://encrypted-tbn0.gstatic.com/images?q=tbn:ANd9GcR50FL9ZZCA7obxNvVLX8sLc0ApLEY3WfhgSvuNSU3yR7YoziXFUQ
Golden Gate Bridge, San Francisco, CA
27,572 strands in each main cable

https://upload.wikimedia.org/wikipedia/commons/0/0c/GoldenGateBridge-001.jpg
https://www.periodicproducts.com/wp-content/uploads/2015/12/golden_gate_painter-w.jpg
https://media.ktvu.com/media.ktvu.com/photo/2018/04/30/chopper%20gg%20bridge%20inspections%20KTVUBCME01.mpg_10.42.08.16_1525116945152.png
_5432510_ver1.0_640_360.jpg
Mercier Bridge, Montreal, Canada
The cost of corrosion is significant

• Infrastructure
– Highway bridges, Gas & liquid transmission
pipelines, Waterways and ports, Airports,
Railroads
• Utilities
– Hazardous materials storage, Electrical
utilities, Telecommunications, Gas
distribution, Drinking Water and sewer
systems
• Transportation
– Motor vehicles, Ships, Aircrafts, Railroad
cars, Hazardous material transport
• Production and manufacturing
– Oil and gas exploration and production,
Mining, Petroleum refining, Chemicals, Pulp
Corrosion cost split-up in the USA
and paper, Agricultural production, Food
(FHWA 1998) processing, Electronics, Home appliances
• Government
– Defense, Nuclear waste storage
FHWA 1998, George Hays 2004; NACE IMPACT Report 2016; Bhaskaran et al. 2014
The cost of corrosion is significant

• In 2014, the direct cost of corrosion in India was

Rs. 4 lakhs crores/year!
• ~ 3 to 4% of GDP
• Up to 50% of construction budgets
• 50% of structures hit a repair in about 10 years
• 30% of steel is used for repair
• 40% of cement is used for repair
A corrosion protection strategy to
minimise the repair and maintenance costs is a MUST

Now, technology is available to achieve long corrosion free service life.

FHWA 1998, George Hays 2004; NACE IMPACT Report 2016; Bhaskaran et al. 2014
India is witnessing a construction boom

• Highways
• Seaports
• Airports
• Urban - Residential & commercial
buildings
• Rural – Many minor projects

We have huge tasks of maintaining

the aging infrastructure and constructing 8
new, durable infrastructure systems
Corrosion map of India

• Local exposure must be considered (say, chemical plants)

• Carbonation governs corrosion when there are no chlorides.
https://www.nbmcw.com/tech-articles/repairs-rehabilitation/39517-india-s-repair-industry-needs-a-responsibility-criteria.html
 Why does iron corrode?

2O2 + 4 H 2O + 4 Fe ® 4 Fe(OH )2

4Fe(OH )2 + O2 + 2H 2O ® 4Fe(OH )3

Iron Ore Rolling/ other manufacturing

(Fe2O3) Blast Furnace Molten material processes

“Dust to dust . . . back to its lowest energy state”

Corrosion = Extractive metallurgy in reverse

3. 4Fe(OH )3 ® 2Fe2O3 + 6H 2O

2. 4Fe(OH )2 + O2 + 2H 2O ® 4Fe(OH )3

1. 2O2 + 4H 2O + 4Fe ® 4Fe(OH )2

Exposure conditions
Steel – An Introduction

• Ferrous alloys with various elements are used for

making reinforcing steel Element Concentration (%)
Mild steel TMT steel Prestressing
steel
Cu 0.27 0.16 0.02
Co - 0.02 0.01
Al - 0.03 0.04
Ni 0.09 0.15 0.02
Mo 0.02 0.06 -
Cr 0.08 0.24 0.27
S 0.05 0.01 -
P 0.06 0.08 0.06
Mn 0.64 0.63 0.83
Si 0.26 0.24 0.29
C 0.19 0.2 0.84
www.trincoll.edu/~alehman/PhotoENGR232_03SEM.htm Fe remaining remaining remaining
Concrete – An Introduction

• Concrete microstructure and pore solution

– C-S-H
– Ca(OH)2; NaOH; KOH pH = -log10[H+]
– Many other complex
chemical compounds

pH of concrete
Acidic Neutral Alkaline pore solution

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH scale

http://www.scielo.br/scielo.php?pid=S1516-14392002000300012&script=sci_arttext
 When does iron corrode?
Pourbaix diagram

• At 25oC

Typical ranges of
potential of steel
in concrete

Rivetti et al. (2017)

Why steel embedded in uncontaminated
concrete does not corrode?
• Steel does not corrode due to
high pH of concrete pore
solution
• A protective layer (“Passive
film”) is formed Passive film
– A thin, invisible, and stable
layer of initial corrosion
products (i.e., iron oxides
and hydroxides).
• However, corrosion can occur when exposed to aggressive
conditions

Hoar (1967)
 Three conditions must exist for reinforcing steel to corrode
Depassivation/corrosion can occur when
exposed to chlorides ands carbon dioxide.
• In the presence of moisture & oxygen (essentials)
What are the essential parts of a corrosion
cell?

ELECTROLYTE

METAL

Note: “Current” flows in the opposite direction as the “electrons” move.

http://www.corrosion-club.com/images/corrosioncell.gif
What are typical electrochemical half-cell
reactions associated with steel in concrete?

• Anodic (oxidation) reaction

2+ -
Fe ® Fe + 2e

• Cathodic (reduction) reaction

1
O2 + H 2O + 2e- ® 2(OH )-
2 Wet-dry
region
Corrosion of Steel in Water with Oxygen

Water
2OH -
2OH - Fe 2+
Fe 2+
1 O + H O + 2e - ® 2OH -
2 2 2
Fe(OH)2
Cathode 2e-
2e-
Anode
Iron
Fe ® Fe 2+ + 2e -

Anode & cathode coexist on the same piece of metal!

How is this brought about on the same piece
of metal?

• In addition to the presence of an electrolyte – there

must be a potential difference between the anode
and cathode.
• The following may also cause local differences in
potential
– Non-uniformity of the metal
– Non-uniformity of the electrolyte
– Non-uniformity in the physical conditions
a. Non-uniformity of the microstructure of
steel can cause local potential differences

• Corrosion potential (Ecorr) of cementite (Fe3C) is

significantly different from the Ecorr of ferrite
– Difference in Ecorr leads to corrosion

Ferrite e- Fe2+
Fe3C
e- Fe2+
Ferrite e-
Fe3C Fe2+

e- Fe2+
Ferrite
Microstructure of steel

https://www.totalmateria.com/images/Articles/kts/Fig419_5.jpg
b. Non-uniformity of the electrolyte
concentrations

Anode
Cl -
H+

-
H+ Cl - Cl
Anode

Anode
H+
H+ Cl -
H+ Cl - Cl -
H+ H+
H+
pH chlorides corrosion inhibitor
(i.e. hydrogen) (e.g. sodium chloride) (e.g. calcium nitrite)

Courtesy: Prof. David Trejo

c. Non-uniformity in the physical conditions

Mould

Steel

Mould

Mill scale

Mould

Irregularities at the steel surface

(mill scale) can cause corrosion,
say, crevice corrosion
Pillai (2003)
c. Non-uniformity in the physical conditions

Corrosion initiation at/near the pores/voids

(Pillai & Trejo)

Irregularities at the steel-concrete

interface (micro cracks or air
voids) can cause corrosion
Angst (2017)
Why corrosion of iron/steel causes cracking of
concrete?

When iron/steel corrodes,

its volume increases by
approximately 6 times

Poursaee (2016)
Corrosion-induced cracking of stone columns
in Roman structures

Colosseum, Pula, Croatia

Expansive pressure can be

so high to crack even stone!
Corrosion-induced
cracking à delamination à spalling
Corrosion-induced
cracking à delamination à spalling
Dripping of water from clothes
led to the acceleration of
corrosion in this case.
Summary

• Cost of corrosion
• Need for corrosion management
• Fundamentals of corrosion
– Pourbaix diagram
– Non-uniformity of metal, concrete, and physical
conditions
– Expansive nature and cracking

Influence the next generation civil engineers to design

not only for strength,
but also for durability with minimum maintenance.

Courtesy: Prof. David Trejo, Oregon State University

References

• Angst, U. M., Geiker, M. R., Michel, A., Gehlen, C., Wong, H., Isgor, O. B., Buenfeld, N.
(2017). The steel–concrete interface. Materials and Structures/Materiaux Et
Constructions, 50(2)
doi:10.1617/s11527-017-1010-1
• Bhaskaran R., Bhalla L., Rahman A., Juneja S., Sonik U., Kour J., Rengaswamy N. S.,
An Analysis of the Updated Cost of Corrosion in India, Material Performance,
NACE International (2014)
• Fontana, Mars G. and Greene, Norbert D. Corrosion engineering /
Mars G. Fontana, Norbert D. Greene McGraw-Hill New York 1978
• Gardoni, P., Pillai, R.G., Hueste, M.D., Reinschmidt, K.F., and Trejo,
D., “Probabilistic capacity models for post-tensioning strands calibrated using laboratory
results,” ASCE Journal of Engineering Mechanics, 135 (9): 906-916, September 2009
• G. Koch, J. Varney, N. Thompson, O. Moghissi, M. Gould, J.
Payer, International Measures of Prevention, Application, and Economics of
Corrosion Technologies Study, NACE International (2016) 1–
30. http://impact.nace.org/documents/Nace-International-Report.pdf.
References

• https://www.fhwa.dot.gov/engineering/geotech/library_sub.cfm?keyword=020
• Hoar, T.P., The production and breakdown of the passivity
of metals (1967) Corrosion Science, 7 (6), pp. 341-355
• Marianna Luna Sousa Rivetti, José da Silva Andrade
Neto, Nilson Santana de Amorim Júnior and Daniel Véras Ribeiro
(December 20th 2017). Corrosion Inhibitors for Reinforced Concrete, Corrosion
Inhibitors, Principles and Recent Applications, Mahmood Aliofkhazraei, IntechOpen, DOI:
10.5772/intechopen.72772. https://www.intechopen.com/books/corrosion-inhibitors-
principles-and-recent-applications/corrosion-inhibitors-for-reinforced-concrete
• Poursaee, A. (2016). Corrosion of steel in concrete structures. Corrosion
of steel in concrete structures (pp. 1-294) doi:10.1016/C2014-0-01384-6
• Poursaee, A. (2016). Corrosion measurement and evaluation techniques
of steel in concrete structures. Corrosion of steel in concrete structures (pp. 169-
191) doi:10.1016/B978-1-78242-381-2.00009-2
• Poursaee, A. (2016). Corrosion of steel in concrete structures. Corrosion
of steel in concrete structures (pp. 19-33) doi:10.1016/B978-1-78242-381-2.00002-X
• Trejo, D., and Pillai, R.G., “Accelerated chloride threshold testing: Part I – ASTM A615
and A706 reinforcement,” ACI Materials Journal, 100 (6): 519-527, November 2003