Half Cell Potential PDF
Half Cell Potential PDF
Half Cell Potential PDF
1. PREFACE
Corrosion of steel in concrete is one of the major
problems with respect to the durability of reinforced
concrete structures. The majority of concrete structures
perform well even after a long period of use in normal
environments. However, there are various reinforced
concrete structures important for our infrastructure,
especially bridges and buildings, which exhibit premature
damage due to environmental actions (EN 206). In contrast
to mechanical actions (as load, wind, etc.) the
environmental actions are not reversible and accumulate
hazardous components (as e.g. chloride ions) in the
concrete. A high percentage of the damages is caused by
insufficient planning, wrong estimation of the severity of
environmental actions and by bad workmanship and thus
many of these structures need to be repaired after a short
service life. In most industrial countries, repair and
restoration of reinforced concrete structures today is nearly
as important as new constructions.
Due to the importance of the problem, RILEM set up an
initial committee on reinforcing steel corrosion in 1960. A
second committee related to the problem, TC 60-CSC
1359-5997/03 RILEM
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RILEM TC 154-EMC
Following the work of TC-124, RILEM set up a
Technical Committee 154-EMC on Electrochemical
Techniques for Measuring Corrosion of steel in concrete.
During the first meeting of the committee it was decided to
prepare RILEM Technical Recommendations on
- Half cell potential measurements
- Test methods for on-site corrosion rate measurements
of reinforcement by means of the polarization
resistance
- Test methods for on-site measurement of resistivity of
concrete
- Embedded Probes for Corrosion monitoring
These documents are presently prepared for publication.
This Draft RILEM Technical Recommendation on Half-Cell
potential measurements intends to give a general description
of half-cell potential measurements for assessing the
corrosion risk of an existing structure (inspection), for
locating precisely corroding rebars prior to and during repair
work and for evaluating the effectiveness and durability of
the repair work. Special attention will be paid to factors
influencing potential measurements and to the interpretation
of potential readings.
2. SCOPE
4. DEFINITIONS
5. THEORETICAL BACKGROUND OF
HALF-CELL POTENTIAL MEASUREMENTS
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Fig. 1 - Evans diagram for uniform corrosion (a) and for a corrosion
couple with ohmic drop (b). Ecorr = corrosion potential, Eeq =
equilibrium potential, icorr = corrosion current density.
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RILEM TC 154-EMC
reproducible potential versus the standard hydrogen electrode
(SHE) are used:
Copper / copper sulfate sat
CSE
Calomel (Hg / Hg2Cl2) KCl sat. SCE
Silver chloride (Ag / AgCl) KCl
SSCE
sat.
+ 0.318 V SHE
+ 0.241 V SHE
+ 0.199 V SHE
Influence of pH
No systematic trends are found with respect to the influence
of pH when using different cement types or additions of
microsilica. From experience it is known that the potentials of
steel in concrete containing slag cements are more negative
compared to OPC concretes.
Cover depth
The potential difference between the position above the
anode and a distant cathode becomes smaller with
increasing cover depth - thus the location of a small
corroding spot becomes more difficult with high cover
depth (Fig. 3) [5]. On the other side, these potential
gradients can indicate if a corroding area is located near the
surface or at rebars deep in the concrete.
+0.2 .... 0 V
dry concrete
+0.2 .... 0 V
Concrete resistivity
The macrocell current affects the potentials of the cathode
(passive steel): the anode is polarizing the passive rebars in the
vicinity of the corroding spot to more negative potentials
(Fig. 4). This shift of potentials to more negative values is
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6. PRACTICAL EXECUTION OF
MEASUREMENTS
6.1 Measurement arrangement
The measurement of half-cell potentials is based on the
electrical and electrolytic continuity between rebars in
concrete, reference electrode on the concrete surface and
voltmeter (Fig. 5).
6.1.1 Voltmeter
The voltmeter should have a high input impedance so
that the current flowing through the reference electrode
does not disturb the stability of the reference electrode
potential. In general the current should not exceed about
10 pA. For measurements on normal outdoor concrete the
minimum acceptable input impedance is 10 M:.
The connections to the voltmeter should be made as
follows: the reference electrode is connected to the negative
terminal, the reinforcing steel to the positive terminal of the
voltmeter. In this arrangement half-cell potential readings
generally will be negative. The occurrence of positive
potentials is possible on passive rebars in dry concrete.
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RILEM TC 154-EMC
6.4 Procedure
Potential measurements can be performed with a single
electrode (point measurements) or with one or several
wheel electrodes (potential mapping).
Inhomogeneous surface conditions as e.g. wet and dry
areas or not embedded rebars that are encountered should
be located on a sketch in order to facilitate the
interpretation of potential readings.
For a statistical evaluation of the data (cumulative
probability plot, histogram) the grid spacing must be kept
constant.
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RILEM TC 154-EMC
small (5 mV or 10 mV, according to the total number of
readings) and the number of readings N(E) is plotted versus
the potential E. The frequency distribution gives a first
impression on mean value of potential, distribution and
skewness. It may be used to compare different parts of a
structure (e.g. two lanes of a bridge deck, different oriented
facades etc.). From the frequency distribution the presence
and percentage of actively corroding and passive rebars can
be estimated.
Cumulative frequency distributions are obtained by
summing up the frequency distribution and plotting the values
6 N(E) versus the potential E on a probability plot (Fig. 9). A
single gaussian distribution would appear as one straight line.
Usually, two or three straight lines with different slopes are
obtained indicating the passive and active distribution of
potentials. Due to the (usually) much higher number of
readings of passive potentials, this distribution is defined
better. From the cumulative probability plot the border value
of potential (90% or 95% passive) can be determined.
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due to the fact that chlorides are transported more easily into
concrete with a lower resistivity (more open pore structure),
high chloride concentrations depassivate the rebars and active
potentials are measured. Points with low resistivity but passive
potentials (Fig. 11) can be interpreted as areas with a high
corrosion risk for the future. Areas with high concrete
resistivity and potentials in the passive range are not affected
by chloride ingress.
The moisture content of the concrete may vary from one
part of the structure to another, an example is given from the
carriageway in an alpine tunnel (Fig. 7). The dilatation joints
are all leaking, thus the concrete in the vicinity of the joints is
wet, highly chloride contaminated and the reinforcement is
actively corroding. Further away from the dilatation joints the
concrete is very dry, no chlorides penetrate and the rebars are
passive. Inhomogeneous moisture distribution enhances the
potential differences between the corroding and passive zones.
As shown above, half-cell potential and resistance data
may be combined to give an overview of various factors
relevant to corrosion risk. However, interpretation requires
taking into account particular features of the structure under
study and cannot be considered straight forward.
The influence of carbonation is twofold: due to the loss of
the concentrated alkaline pore solution the pH of the pore
solution is much lower and carbonated concrete, often
sheltered from rain, shows high resistivity. This influences
both the absolute values of the potentials measured from the
concrete surface and the possibility of locating small corroding
areas. In high resistive media as carbonated concrete, the
location of small corroding areas will be more difficult. Halfcell potential measurements taken on concrete structures with
high resistive surface layers due to carbonation show more
positive potentials of both, passive and corroding rebars.
As mentioned before, high resistive surface layers may
make correct interpretation very difficult.
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RILEM TC 154-EMC
154-EMC) or for sample locations for destructive analyses.
Finally, they can be used to select the positions for embedding
sensors . In all cases, the number of measurements or sensors
can be minimised and the results integrated in a rational way
into the overall picture of the structure.
7.2.3 Control the effectiveness and durability of a
restoration work
There are different repair options for corroding reinforced
concrete structures. Some of them intend to bring the steel in
a non-corroding or passive condition. Thus half-cell potential
measurements can be used in principle to evaluate the
effectiveness and the durability of the repair work. Usually
this requires a potential survey on the same areas as
performed during inspection (prior to repair). The
interpretation of the overall success of the repair work can be
evaluated best on the basis of the cumulative probability plot;
plotting the potential map made after repair will show areas
where steel is still corroding.
o
Inhibitors
Testing the efficiency of inhibitors penetrated from the
concrete surface with half-cell potential measurements is
difficult [21]. Changes in the pore water composition and thus
the concrete resistivity as well as different possible
mechanisms of the inhibitor action (anodic, cathodic, mixed,
blocking...) can lead to shifts of the half-cell potential measured
from the concrete surface that cannot be interpreted straight
forward. More research is needed before potential mapping may
allow unambiguous evaluation of inhibitor treatment.
In consequence, the following points should be taken
into account when assessing the efficiency and durability of
repair work with half-cell potential measurements:
Electrochemical realkalization
Half-cell potential measurements can be used to evaluate
the corrosion state of the rebars after electrochemical
realkalization. The results on a test site [20, 21] have shown
that the potential values after the treatment (after waiting three
months in order to allow depolarization) were shifted by about
0.2 V to more negative values. Any straightforward, simple
interpretation more positive potentials = repassivation fails.
The decrease in potentials is due to two effects: after the
realkalization treatment, the concrete resistivity is much lower
due to the presence of a quite concentrated sodium
(bi)carbonate solution in the pores and the alkalinity around
the rebars has strongly increased (from about pH 9 to 13). The
Time of measurement
The waiting time prior to perform measurements after
repair work has to be defined according to the type of repair:
electrochemical restoration techniques (ECR, ER) lead to a
strong cathodic polarization of the rebars, the time to
depolarize can be between one and several months according
to the oxygen access to the rebars. New concrete or repair
mortar instead require time to hydrate and dry out partially.
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Shift in potential
The shift in potential (before and after repair) depends on
the type of repair technique applied and its mechanistic action.
Half-cell potential mapping can be used to evaluate the
effectiveness and durability of repair works with the normal
interpretation only when the concrete resistivity is not changed
too much by the treatment.
o
Corrosion state
Corroding areas of the structure require more protection
current than areas with passive steel, due to the lower
polarization resistance the current will flow preferentially in
the corroding regions.
o
Concrete resistivity
The protection current will follow the low resistive
pathways, thus in areas with very humid or wet concrete
will flow more current.
Based on half-cell potential maps the corroding zones can
be identified and the layout of the anodes can be optimized:
critical areas can be protected by isolated anodes and
connected separately to the rectifier or the amount of anode
material (two or three layers of anode mesh) can be increased in
order to comply with the high current density expected. The
final draft version of European Standard EN12696 states that
potential mapping must be carried out on representative areas, in
particular for locating spots for reference electrodes to be placed.
8. REPORT
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REFERENCES
[1] RILEM TC 60 CSC, Corrosion of Steel in Concrete, ed. P.
Schiessl, Chapman and Hall, London (1988).
[2] Page, C.L. and Treadaway, K.W.J., Aspects of electrochemistry
of steel in concrete, Nature 297 (1982) 109-115.
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