Corrosion

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.
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
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.
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
Double layer
Corrosion damage
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.
Electrochemical process of steel
corrosion in concrete
Volumetric change
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 copper-copper sulfate
electrode.
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)
Corrosion probability
>-200 Low, less than10% probability
of corrosion
-200 ~ -350 Uncertain
<-350 High, greater than 90% probability
of corrosion
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.
Results affected by
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.
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.
Polarization curve
Deviation from the steady-state condition
can be expressed by the electrode
polarization potential, also known, as
overpotential (a or c) where
corr a
E E =
E E
corr c
=
Polarization curve
Polarization Resistance
The slope at the origin of the polarization
curve is defined as the polarization
resistance, Rp:
( )
c a corr
c a
0
c , app
p
i 3 . 2 i d
d
R
+

=

=

Measurement
Polarization resistance curve
Typical polarization resistance for
steel in concrete

Rate of corrosion
Polarization resistance,
R
p
(k.cm
2
)
Corrosion penetration,
p (m/year)
Very high 0.25 < R
p
< 2.5 100 < p < 1000
High 2.5 < R
p
< 25 10 < p < 100
Low/moderate 25 < R
p
< 250 1 < p < 10
Passive 250 < R
p
p < 1

Experimental set-up
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.
Electrochemical Impedance
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
Voltage response, V, to sinusoidal
current signal i.
time
V (t)
i (t)
V or i
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-
frequency-dependent 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.
Model of equivalent circuit
Nyquist plot for the impedance of
the electric circuit