Corrosion of Reinforced Concrete

Ha-Won Song
Professor
School of Civil and Environmental Engineering
Yonsei Univ., Seoul 120-749, KOREA

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Introduction
When a metal is inserted in an aqueous environment, a
potential difference develops at the metal-aqueous solution
interface.
The rate at which the reactions and the movement of
charges across the interface occurs is determined by the
magnitude of the potential difference.
In aqueous solution, the distribution of particles close to the
metal surface is no longer homogeneous, nor are the forces
isotropic.

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Double Layer
Water molecules are polar and therefore are attracted to the charged
surface and orient themselves along the interface. Charged ions can also
form hydrated units. In analogy with a parallel-plate condenser, the
system of the two oppositely charged planes is referred to as a double
layer

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Double Layer
Small ions generate large Coloumb forces, and therefore have
greater chance to become hydrated.
This means that most cations () are solvated and most
anions ( ), being large, are not solvated. This also
explains why some anions cause more corrosion damage.
The large anions are unhydrated and can get closer to the
metal surface, even though they may not participate directly
in the corrosion reactions.

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Double layer

The ion can be adsorbed on the metal surface forming an

inner-sphere complex when no water molecule is between
the surface function group and the ion, or an outer-sphere
complex when at least one water molecule exists between
the surface and the ion. Ions can also be adsorbed in the
diffuse swarm of the double layer in order to neutralize the
surface charge
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Corrosion of reinforced concrete

Corrosion of reinforcing bars in the electrolytic concrete pore
solution involves electron or charge transfer through the
chemical reactions at the interface. Electrode potential
difference between the reinforcing bars and electrolyte is the
driving force for the charge transfer to occur.

Corrosion damage

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Electrochemical process of steel corrosion in

concrete

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Volumetric change

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Carbonation of Concrete
Painting with Phenolphthalein

Concrete exposed to CO2

Carbonated concrete

(accelerated test)

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Corrosion due to Carbonation

CO2

CO2

CO2

CO2

CO2

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Corrosion due to chlorides

Cl-

ClCl-

Cl-

Cl-

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Factors needed for steel corrosion

H2O

O2

O2

H2O

O2

H2O

Cover concrete quality, W/C

pH

cracks

H2O

+ humidity

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Corrosion Potential
The corrosion potential of the steel in reinforced concrete
can be measured as the voltage difference between the
steel and a reference electrode in contact with the surface
of the concrete. Half-cell measurements may be made
relatively easily, using only a high impedance voltmeter
and a standard reference electrode, such as a coppercopper sulfate electrode.

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

System for
measuring the
half-cell
potential

The potential recorded in the half-cell measurement can

be used to indicate the probability of corrosion of the steel
reinforcement.
Measured potential
(mV vs. CSE)
>-200
-200 ~ -350
<-350

Corrosion probability
Low, less than10% probability
of corrosion
Uncertain
High, greater than 90% probability
Concrete
Materials, Mechanics &
of
corrosion
Engineering Lab., Yonsei Univ.

Results affected by
Degree of humidity in concrete. The measurement is very
sensitive to the humidity existing in the concrete. More
negative potentials result for concrete with higher degree of
saturation.
Stray currents. The presence of stray currents will
significantly affect the measurements of the half-cell potential.
Oxygen content near the reinforcement. The lack of
oxygen near the reinforcement results in more negative
potentials as compared to more aerated zones.
Microcracks. Localized corrosion can be generated by
microcracks, which also modify the concrete resistivity,
consequently affecting the corrosion potential measurement.
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Polarization curve
Electrode potential difference between the reinforcing bars and
electrolyte is the driving force for the charge transfer to occur.
Their electrode potentials will change with the corrosion
reaction rate until a stable or equilibrium state (Ecorr) is
achieved. At this potential the anodic (ia) and cathodic (ic)
current densities are opposite and equal and to icorr.
Deviation from the steady-state condition can be expressed by
the electrode polarization potential, also known, as
overpotential (a or c) where

a = E E corr
c = E corr E
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Polarization curve

a = E E corr
c = E corr E

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Polarization Resistance
The slope at the origin of the polarization curve is
defined as the polarization resistance, Rp:

a
c

Rp =
=
di

app ,c 0 2.3 i corr ( a + c )

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Tafels extrapolation technique corrosion rate

Icorr

corrosion rate

anodic curve slop

cathodic curve slop

RP

polarization resistance

-100

Anodic curve

-200
Potential(mV)

I corr

a c
=
2 .3 R P ( a + c )

-300

Corrosion potential

-400

Cathodic curve

-500
-600
0.01

0.1

1
10
Current()

100

Corrosion rate

Tafels extrapolation technique

Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

1000

Measurement

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Polarization resistance curve

Typical polarization resistance for steel in concrete

Rate of corrosion
Very high

Polarization resistance,
Rp (k.cm2)
0.25 < Rp < 2.5

Corrosion penetration,
p (m/year)
100 < p < 1000

High
Low/moderate
Passive

2.5 < Rp < 25

25 < Rp < 250
250 < Rp

10 < p < 100

1 < p < 10
p<1

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Experimental set-up

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Electrochemical Impedance
Electrochemical impedance spectroscopy, or AC impedance,
is an informative method because not Rp only is measured,
but also the physical processes in concrete and steel/
concrete interface are assessed. Impedance measurement
employs small-amplitude alternating (AC) signals in a wide
range of frequency as a perturbation.
In electrochemical impedance spectroscopy measurements, a
sine or cosine wave of AC current with magnitude I0 and
frequency f is commonly used as the input. The output is
recorded as a voltage response with the magnitude V(f) and a
phase angle (f) with respect to the current
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Voltage response, V, to sinusoidal current signal i.

V (t)
i (t)

V or i

time

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Equivalent circuit
Equivalent circuits have been used to model the impedance of
complex systems.
Pure resistance and pure capacitance represent two types of
impedance to the charge transfer.
Energy is dissipated through electrons or ions flowing through a
resistance element, which constitutes a non-frequencydependent impedance that has only a real part.
A capacitance element represents an energy storage process or
charge separation under an electrical field. It creates an
alternating electric current under an alternating electrical field,
and the impedance will decrease with frequency.
Concrete Materials, Mechanics &
Engineering Lab., Yonsei Univ.

Model of equivalent circuit

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Nyquist plot for the impedance of the electric circuit

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.

Representation of the cracking-corrosion-cracking cycles

Concrete Materials, Mechanics &

Engineering Lab., Yonsei Univ.