Corrosion mechanisms, Control, and

Monitoring in Concrete Structures

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

http://picasaweb.google.com/sudipmoitra67/NEWS_PIX#5354282213058954946

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.
• The bridge was replaced with a
segmental, post-tensioned bridge in
1987.
• Only 13 years later, a post-tensioned
tendon on the new bridge failed.
• If two tendons fail, a PT bridge can
collapse (Pillai 2009).

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Golden Gate Bridge, San Francisco, CA

27,572 strands in each main cable

Mercier Bridge, Montreal, Canada

2
The cost of corrosion is significant

• In 2012, the direct cost

of corrosion in India was
Rs. 2 Lakh crores/year!

A corrosion protection strategy

to minimise the
repair and maintenance costs
is a MUST

Corrosion cost split-up in the

USA (FHWA 1998)

FHWA 1998, George Hays 2004

Why does iron corrode?

2O2  4 H 2 O  4 Fe  4 Fe OH 2

4 Fe OH 2  O2  2 H 2 O  4 Fe 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. 4 FeOH 3  2 Fe2O3  6 H 2O

2. 4 FeOH 2  O2  2 H 2O  4 FeOH 3

1. 2O2  4 H 2O  4 Fe  4 FeOH 2
Exposure conditions

3
Concrete – An Introduction

• Concrete microstructure and pore solution

– C-S-H
– Ca(OH)2; NaOH; KOH
– Many other complex
chemical compounds

pH = -log10[H+]

Acidic Neutral Alkaline pH of concrete

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

Steel – An Introduction

• Ferrous alloys with various elements such as

C, Mn, P, S, Si, Ni, Mo, Cr, V etc.

www.trincoll.edu/~alehman/PhotoENGR232_03SEM.htm

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Common Types of Reinforcing Bars

• Plain and ribbed (hot rolled) mild steel bars

– The ribs improve the mechanical bond.
• Cold twisted deformed (CTD) bars
– Ribbed low carbon steel bars, twisted to increase the yield strength
by work hardening. The resistance to corrosion decreases due to the
residual stresses caused by the work hardening.
• Thermo-mechanically treated (TMT) bars
– Bars with hard high strength surface and a ductile core.
• Corrosion-resistant TMT bars
– Bars with small quantities of copper and chromium, and higher than
usual percentage of phosphorus.
• Galvanised bars, Epoxy-coated bars
• Stainless steel bars (>10.5% chromium)
• Prestressing strands

Thermomechanically Treated (TMT)

or Quenched and Tempered (Q&T) Bars
• Process • After hot rolling to the
desired size and shape, the
low carbon steel bars are
quenched with water and
then cooled.
• Quenching converts the
surface layer to (hard)
martensite while the core
remains as austenite.
• As the bar cools, heat flows
(Log scale)
• Effect
from the core to the surface
layer turning it to tempered
martensite. The core
transforms to ductile ferrite-
pearlite.

Varghese

5
Prestressing strands

Sheathed strand Coated strand

Uncoated strands of various sizes

http://image.made-in-china.com/2f0j00DvmTwkJGLouV/PC-Strand-2.jpg
http://www.tootoo.com/buy-unbonded_pc_steel_strand/
Strands supplied in coils
http://www.maklada.com/en/site/toron_acier_beton.htm

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
– 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)

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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 the corrosion of steel in concrete?

• Anodic (oxidation) reaction

Fe  Fe2  2e

• Cathodic (reduction) reaction

1
O2  H2O  2e  2(OH )
2

http://www.corrosion-club.com/images/corrosioncell.gif, http://www.tfhrc.gov

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Corrosion of Steel in Water with Oxygen

Water
2OH -
2OH -
Fe 2+ Fe 2+
1 O2  H2O  2e  2OH 
2 Fe(OH)2
Cathode
2e- 2e-
2 
Fe  Fe  2e
Iron Anode

Anode & cathode coexist on the same piece of metal !

Two major types of corrosion in concrete structures

• Carbonation-induced corrosion
– General or uniform section loss

• Chloride-induced corrosion
– Localized, pitting or non-uniform section loss

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Carbonation-induced corrosion

• CO2 + H2O  H2CO3 (carbonic acid)

• H2CO3 + Ca(OH)2  CaCO3 + 2•H2O
• C-S-H will liberate CaO, which will carbonate as follows.
• H2CO3 + CaO  CaCO3 + H2O
• This leads to a reduced pH
at which the passive layer is
unstable
• This results in active corrosion
of the embedded steel

http://www.nbmcw.com/articles/concrete/others/493-carbonation-a-
durability-threat-for-concrete.html

Carbonation-induced corrosion

http://www.nbmcw.com/articles/concrete/others/493-carbonation-a-
durability-threat-for-concrete.html

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Chloride-induced corrosion

Cl -

Flaws in passive layer Pits growing at

and high chloride content various locations

Chloride-induced corrosion

Concrete
FeCl2 + 2H2O  2HCl + Fe (OH)2
1 O  H O  2e   2OH 
2 2 2

Fe 2+ + 2Cl -  FeCl2 2H + + 2 Cl -

2e-
Iron 2e  Fe2  Fe

• The process is regenerating and instead of spreading along

the bar, corrosion continues at local anodes and deep pits
are formed.

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Critical chloride threshold can be different for
different steels
Critical Chloride Threshold Value, (lb/yd )

Critical Chloride Threshold Value, (kg/m )

25
3

15

20 12

15 9

10 6

5 3

0
0

3
A706 A615 Microcomposite SS304 SS316

Pillai and Trejo 2005

Typical locations for chloride induced corrosion and

solutions?

http://is2c.nl/project-10979/moisture-and-salt-transport/

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Typical locations for chloride induced corrosion and
solutions?

Stress Corrosion

• Stress corrosion or stress corrosion cracking results from

the combined action of tensile stress and a corrosive
environment.
• Many materials become susceptible to a corrosion under
stress. Small cracks form and propagate leading
eventually to brittle failure.
• The stress need not be externally applied
• Residual stress due to previous mechanical
or thermal actions.
• Post-tensioning strands
• Welded joints

Intergranular stress
corrosion cracking in brass

Callister

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Stress Corrosion

Chloride stress corrosion cracking in this 304L stainless

steel weldment due to the residual stresses from weld

Most of the metal surface is unattacked, while fine

cracks propagate through the cross section –
resulting in failure without warning

A micrograph showing transgranular cracks

due to chloride stress corrosion cracking

http://www.thefabricator.com/article/metalsmaterials/combating-plate-corrosion
http://www.volpe.dot.gov/coi/pis/work/archive/tankcar.html

Galvanic corrosion

•When pairs of metals are immersed

in an electrolyte, one will become the
anode and the other the cathode.
•For example, in sea water, the
relative ease with which a metal can
corrode is indicated in the table.
•This implies that in a fitting made of
mild steel and brass, the mild steel
part would corrode in sea water,
whereas if the fitting was made of
stainless steel and brass, the brass
part would corrode.

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Galvanic corrosion

http://www.ecr6.ohio-state.edu/mse/mse205/lectures/chapter18f/index_chap18.htm

Corrosion due to differential oxygen availability

• Sometimes the change in the composition of

the electrolyte (e.g., concentration of
dissolved oxygen) causes preferential
corrosion in one part of immersed body.
• For example, in a riveted or bolted junction,
the areas that are inaccessible will become
the anode and corrode since the electrolyte
there is poorer in dissolved oxygen.
• Similarly, in steel piling in stagnant water,
the surface layers of water are rich in
oxygen whereas the lower layers are oxygen
deficient. Consequently, the lower layers are
anodic and corrode locally.
• Also, in pitting corrosion, the bottom of the
pit is anodic since it is the region poorer in
oxygen. Consequently, the pit becomes
deeper leading premature failure of the
member. Illston & Domone, Callister; http://www.amteccorrosion.co.uk

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Why steel corrosion causes cracking of concrete?

Fe
FeO
Fe2O3
Fe(OH)2
Fe(OH)3
Fe(OH)3·3H2O

When steel corrodes, its volume increases by

approximately 6 times

Corrosion resistance steels

165 tons of 2205 (duplex) stainless Stainless steel rebar on a bridge

rebar were supplied for the new ramp deck of the 407 Highway, Toronto.
of the Garden State Parkway in New
Jersey (1998)

http://www.stainless-rebar.org/

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Cathodic protection for corrosion prevention

• Based on the reversal of the direction of the metal oxidation reaction.

That is, the metal is “forced” to be the cathode.
• Electrical current to supply the extra electrons
• The metal to be protected is connected to the negative terminal of a
battery and a scrap anode is connected to the positive terminal.
• Connecting to a bag of magnesium powder is also a practice.
• The anode has to be periodically replaced as it will be eventually
consumed. This problem is reduced by covering the protected metal with
plastic to reduce the cathodic area.

Schaffer et al.

Cathodic protection for corrosion prevention

(cont’d)
• Sacrificial anode
– A more anodic metal, such as Zn and Mg, is
placed in contact with the metal to be
protected.
– Corrodes rapidly and only protects the cathodic
material close to it. Therefore, many sacrificial Bridge deck with point anodes (pucks)
anodes have to be used to cover large areas
and they have to replaced often.
• Sacrificial anodes are widely used in
marine environments (say, offshore
platforms).

Offshore riser with sacrificial anodes

A sacrificial anode undergoing

preferential corrosion Schaffer et al., Illston & Domone

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Coatings for Corrosion Prevention

• Anodic metal coatings

– Steel can be protected by Zn coatings, which will continue to protect
the steel even after the coating is scratched (sacrificial anode mode)
• Non-cathodic epoxy coatings
– Protect rebars by limiting the diffusion of oxygen and water.
– A major problem with such coatings is the presence of “pinholes” or
“holidays” – small exposed areas caused accidentally.
– ‘Holidays” can result in the formation of corrosion cells with high
anode-to-cathode area ratios. Many modern coatings incorporate Zn
particles in order to combat this problem.

Schaffer et al.

Corrosion inhibitors

• ACI 116 definition

– a chemical compound, either liquid or powder, usually
intermixed with concrete and sometimes applied to
concrete, and that effectively decreases corrosion of
steel reinforcement
• Admixed corrosion inhibitor for new construction
– Calcium Nitrite based corrosion inhibitor
• Rheocrete® CNI – BASF
• Rheocrete® 222+ – BASF
• DCI® Corrosion Inhibitor – WR GRACE

http://www.netweber.co.uk; http://rebar.ecn.purdue.edu/ect/links/technologies/civil/corrosin.aspx

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Migrating corrosion inhibitors for repair procedures

http://www.netweber.co.uk; http://www.protectivepackaging.net/vapor-corrosion-inhibitors

Hydrophobic pore blockers

1. Pore blocking
– Minimises diffusion of
chlorides, water etc.
2. Corrosion inhibiting
coating at the steel
surface

http://www.hycrete.com/products/how-hycrete-products-work/

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How to detect corrosion in concrete structures?

• ASTM C876 Standard Test Method for Half-Cell

Potentials of Uncoated Reinforcement in Concrete
– If E < -0.35 V, 90% chance of corrosion When using
Cu/CuSO4
– If E > -0.25 V, 90% chance no corrosion reference
– If -0.35 V < E < -0.25 V, then ? electrode

Mehta and Monteiro

Some commercially available equipment to detect

corrosion using potential mapping

• Canin+

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Linear polarization and guard ring technique to
measure corrosion rate

Mehta and Monteiro

Some commercially available equipment to measure

corrosion rate

• GECOR6

Connection to
reinforcement

Photo courtesy: James Instruments

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Corrosion in Concrete - Summary

• In general, the high pH of concrete is sufficient to maintain the steel in a

passivated state. This leads to the spontaneous formation of a stable
protective iron oxide film around the steel. Corrosion occurs only when
these conditions are changed and pH drops.
• Depassivation of the concrete can occur when:
• The calcium hydroxide has been carbonated by the penetration of
CO2 into the concrete (and the pH becomes lower than ≈11).
• Chloride ions are present in the concrete (more than 0.2-0.4%),
even though the pH is high.
• Moisture and oxygen are necessary for corrosion to be sustained.
Porous concrete and cracks permit the ingress of water and oxygen, and
promote corrosion.
• Corrosion inhibitors can be used to prevent corrosion
• Corrosion can be detected using potential measurement
• Corrosion rate can be determined using LPR and Guard ring techniques

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