Corrosion mechanisms, Control, and

Monitoring in Concrete Structures

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.
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).

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

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

Golden Gate Bridge, San Francisco, CA

Mercier Bridge, Montreal, Canada

27,572 strands in each main cable

The cost of corrosion is significant

Why does iron corrode?

In 2012, the direct cost

of corrosion in India was
Rs. 2 lakhs 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)

2O 2 4 H 2 O 4 Fe 4 Fe OH

4 Fe OH 2 O 2 2 H 2 O 4 Fe OH

Iron Ore
(Fe2O3)

Blast Furnace

Molten material

Rolling/ other manufacturing

processes

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

Corrosion = Extractive metallurgy in reverse
3.

4 FeOH 3 2 Fe2O3 6 H 2O

2.

4 FeOH 2 O2 2 H 2O 4 FeOH 3

1.

2O2 4 H 2O 4 Fe 4 FeOH 2

Exposure conditions

FHWA 1998, George Hays 2004

Concrete An Introduction

Steel An Introduction

Concrete microstructure and pore solution

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

Ferrous alloys with various elements such as

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

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

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

Thermomechanically Treated (TMT)

or Quenched and Tempered (Q&T) Bars

Common Types of Reinforcing Bars

Process

Plain and ribbed (hot rolled) mild steel bars

After hot rolling to the

desired size and shape, the
low carbon steel bars are
quenched with water and
then cooled.

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
y the work hardening.
g
residual stresses caused by

Quenching converts the

surface layer to (hard)
martensite while the core
remains as austenite.

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.

(Log scale)

Effect

Galvanised bars, Epoxy-coated bars

Stainless steel bars (>10.5% chromium)
Prestressing strands

Varghese

Why steel embedded in uncontaminated concrete

does not corrode?

Prestressing strands

Sheathed strand

Coated strand

Steel does not corrode

due to high pH of
concrete pore solution
A protective layer
((Passive
Passive film)
film ) is formed
A thin, invisible, and stable
layer of initial corrosion
products (i.e., iron oxides
and hydroxides).

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/
http://www.maklada.com/en/site/toron_acier_beton.htm

As the bar cools, heat flows

from the core to the surface
layer turning it to tempered
martensite. The core
transforms to ductile ferritepearlite.

However, corrosion can occur when exposed to

aggressive conditions
Strands supplied in coils
Hoar (1967)

What are typical electrochemical half-cell reactions

associated with the corrosion of steel in concrete?

What are the essential parts of a corrosion cell?

Anodic (oxidation) reaction

ELECTROLYTE

Fe

Fe2 2e

Cathodic (reduction) reaction

1
O2 H2O 2e 2(OH )
2
METAL

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

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

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

Corrosion of Steel in Water with Oxygen

Two major types of corrosion in concrete structures

Carbonation-induced corrosion

Water

2OH

2OH -

1 O2 H 2O 2e 2OH
2
Fe(OH)2

Cathode

2e-

Fe

General or uniform section loss

Fe 2+

2+

Fe Fe2 2e

Iron

2e-

Anode

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

Anode & cathode coexist on the same piece of metal !

Carbonation-induced corrosion

Carbonation-induced corrosion

CO2 + H2O H2CO3 (carbonic acid)

H2CO3 + Ca(OH)2 CaCO3 + 2H2O
C-S-H will liberate CaO, which will carbonate as follows.
H2CO3 + CaO CaCO3 + H2O
p
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-adurability-threat-for-concrete.html

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

Chloride-induced corrosion

Chloride-induced corrosion
Concrete

Cl -

FeCl2 + 2H2O 2HCl + Fe (OH)2

1 O H O 2e 2OH
2
2 2

Fe 2+ + 2Cl - FeCl2

2H + + 2 Cl -

2e-

2e Fe2 Fe

Iron
Pits growing at
various locations

Critical chloride threshold can be different for

different steels

7-wire strand

Deformed bar

25

15

20

12

15

10

3
0

Critical Chloride Thresshold Value, (kg/m )

Pitting corrosion on strands and deformed bars

due to chloride attack

The process is regenerating and instead of spreading along

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

Critical Chloride Thhreshold Value, (lb/yd )

Flaws in passive layer

and high chloride content

A706

A615

Microcomposite SS304

SS316

Pillai and Trejo 2005

Typical locations for chloride induced corrosion and

solutions?

Typical locations for chloride induced corrosion and

solutions?

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

A huge concern about the epoxy-coated steel

It is more dangerous to
use damaged epoxy-coated steel than
conventional uncoated steel

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
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

Courtesy: M. Thomas

Galvanic corrosion

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

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.

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

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

Why steel corrosion causes cracking of concrete?

Volume of rust is ~6 times more than

that of steel

Fe
FeO
Fe2O3
Fe(OH)
(
)2
Fe(OH)3
Fe(OH)33H2O
When steel corrodes, its volume increases by
approximately 6 times

Corrosion resistance steels

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.

165 tons of 2205 (duplex) stainless

rebar were supplied for the new ramp
of the Garden State Parkway in New
Jersey (1998)

Stainless steel rebar on a bridge

deck of the 407 Highway, Toronto.

Schaffer et al.

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

Cathodic protection for corrosion prevention

(contd)
Sacrificial anode

Coatings for Corrosion Prevention

Anodic metal coatings

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
anodes
d h
have tto b
be used
d tto cover llarge areas
and they have to replaced often.

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

Bridge deck with point anodes (pucks)

Sacrificial anodes are widely used in

marine environments (say, offshore
platforms).

Protect rebars by limiting the diffusion of oxygen and water.

A major problem with such coatings is the presence of pinholes
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.

Offshore riser with sacrificial anodes

A sacrificial anode undergoing

preferential corrosion

Schaffer et al., Illston & Domone

Schaffer et al.

Corrosion inhibitors

Migrating corrosion inhibitors for repair procedures

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

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

Hydrophobic pore blockers

How to detect corrosion in concrete structures?

1. Pore blocking
Minimises penetration
of chlorides, water etc.

2. Corrosion inhibiting
g at the steel
coating
surface

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

Some commercially available equipment to detect

corrosion using potential mapping

ASTM C876 Standard Test Method for Half-Cell Potentials

of Uncoated Reinforcement in Concrete
If E < -0.35 V, 90% chance of corrosion
If E > -0.25 V, 90% chance no corrosion
If -0.35 V < E < -0.25 V, then ?

When using
Cu/CuSO4 reference
electrode

However
However, monitoring the variation is better strategy than
relying on absolute values

Mehta and Monteiro

Linear polarization and guard ring technique to

measure corrosion rate

Canin+

Mehta and Monteiro

Some commercially available equipment to measure

corrosion rate
GECOR6

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.

Connection to
reinforcement

Photo courtesy: James Instruments

Corrosion in Concrete - Summary

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