Corrosion of Steel in Concrete & Assessment Techniques

George Sergi

Introduction
Concrete is a porous material whose pores contain an electrolyte made up
primarily of sodium and potassium hydroxides. 1 Steel reinforcement is normally
protected in such an electrolyte owing to the formation of a dense and uniform
passive oxide film. 2 Carbonation of the concrete (neutralisation of the alkali
constituents by CO 2 gas from the atmosphere), or infestation of the concrete with
salt from seawater or from deicing agents leads to the breakdown of the
protective oxide film and to corrosion of the steel. 3,4 Corrosion of steel in
concrete is an electrochemical process whereby anodic and cathodic reactions
occur simultaneously on the surface of the steel resulting in the dissolution of the
metal at the anodic sites. 5

The corrosion cell

To demonstrate the principles of electrochemical corrosion, let us consider the
simple "Daniel-cell". This consists of zinc immersed in ZnSO 4 solution and
copper immersed in a CuSO 4 solution. The two electrodes are connected to a
variable resistor R, voltmeter V, and ammeter A (Fig, 1). The potential difference
(emf) between the two electrodes when no current is flowing is 1.1 V. If a small
current is allowed to flow through the external resistor (I 1 in Fig. 2), the measured
potential difference falls below 1.1 V because both electrodes polarise, Zn to b
and Cu to e (Fig. 2). As the resistance is decreased, the current increases and
the potential difference decreases until, when the system is short-circuited (the

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resistance is very small), maximum current flows and the potential difference is
almost zero (I max ). The Zn anode polarises along the line abc and the Cu cathode
along the line def. The full polarisation of Zn in volts is given by c-a and for Cu
by f-d.

Figure 1 Polarised copper-zinc cell (Daniel-cell)

Figure 2 Polarisation diagram for copper-zinc cell

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The anodic reaction in the “Daniel-cell” is:

Zn → Zn2+ + 2e-

where Zn corrodes and goes into solution and the cathodic reaction is:

Cu2+ + 2e- → Cu

where copper is deposited from the CuSO 4 solution.

In the case of steel in oxygenated water, the simplified anodic reaction is:

Fe→ Fe2+ + 2e-

Iron atoms undergo oxidation (electron loss) to form F++ ions which pass into
solution. The excess free electrons left in the metal are consumed, converting
oxygen and water to hydroxyl ions in a process of reduction (electron addition)
according to the following cathodic reaction:

½ O 2 + H 2 O + 2e- → 20H-

Cathode
O2 + 2H2O → 4OH
-

- 2FeO.OH + H2O
4e
-
Cl
- OH
- ½O2
Cl ++
2Fe - 2Fe
Anode Cl OH-
-
Cl

Figure 3 Mechanism of corrosion in oxygenated water

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Both the anodic and cathodic reactions occur at adjacent sites simultaneously on
the surface of the steel (Fig. 3). As was the case with the "Daniel..cell", the
anodic and cathodic reactions of steel in water can be represented in a
polarisation diagram (known as an "Evans” diagram), as shown in Fig. 4. The
intersection point of the two lines corresponds to the electrode potential at which
the rates of the anodic and cathodic reactions are equal and is termed the
corrosion potential, (Ecorr), the value that steel adopts when corroding freely.
The magnitude of the anodic and cathodic reactions is represented by the
number of electrons flowing per second between the anodic and cathodic sites
on a unit area of the metal surface and is a measure of the corrosion rate, Icorr. It
is often referred to as the corrosion current density and expressed in electrical
units (amps/m2 of steel area or more commonly, mA/m2). It is the current at the
equivalent point of intersection in Figure 4. Faraday’s laws of electrolysis may be
used to obtain corrosion rates in more familiar terms (average rates of mass loss
per unit area) and these values may be simply converted to average rates of loss
of thickness of metal from knowledge of the density of the steel.

Figure 4 Evans diagram for iron corroding in oxygenated water

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Factors affecting corrosion rates
Both Icorr and Ecorr can vary depending on the degree of polarization of either
the anodic or the cathodic reactions. When polarisation occurs mostly at the
anodes, (i.e. the anodic process is for some reason hindered) it is said that the
corrosion reaction is anodically controlled. Similarly, if the cathodic reaction is
polarised, the corrosion reaction is said to be cathodically controlled. Since the
operation of a corrosion cell depends on three processes occurring in series, viz.
the anodic reaction, the cathodic reaction and the flow of currents through the
intervening electrolyte and metal the overall corrosion rate is not only governed
by the anodic and cathodic reactions but also by the magnitude of the resistance
of the electrolyte which can hinder ionic conduction. This is represented
graphically in Figure 5.

Figure 5 Effect of resistance of the electrolyte

on the corrosion rate of the reinforcement

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Corrosion of steel in concrete
When steel is immersed in an alkaline solution such as sodium or potassium
hydroxide, its surface becomes coated with an adherent, insoluble oxide film
(γ-Fe 2 O 3 ) which is stable over a range of potentials. Its polarisation curve is
modified to that shown in Figure 6 and shows that the corrosion rate over
intermediate potentials becomes very small. 6 Such a situation is termed
passivity, one of the states in which the metal can thermodynamically exist at
variable pH levels of the electrolyte as shown by a simplified Pourbaix diagram
for steel
(Fig. 7). The pore electrolyte of concrete is primarily a mixture of sodium and
potassium hydroxides and as such, the embedded steel attains passivity. The
condition is usually characterised by a value of Ecorr higher than about -250mV
(measured relative to a standard copper/ copper sulphate reference electrode-
CSE scale).

Ecorr
Potential (E)

Passivity

Current (i)

Figure 6 Evans diagram for passive iron in oxygenated alkaline solution

When carbonation of the concrete occurs, whereby the pH of the pore electrolyte
becomes neutral, passivity can no longer be thermodynamically stable and the
steel corrodes as it would in an equivalent neutral solution (Fig. 4). The rate of

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steel corrosion in carbonated concrete is subject to anodic resistance control. 7,8 It
therefore depends critically on the moisture content of the concrete since this is
primarily what determines the electrolytic resistivity of the material. The corrosion
potential of the steel in this condition is typically in the range -450 to -600mV
(CSE scale) when corrosion is occurring.
Potential (NHE Scale), V

Corrosion Passivation
0

-1 Corrosion
Immunity

0 2 4 6 8 10 12 14
pH

Figure 7 Pourbaix diagram for steel

The other main cause of corrosion of reinforcing steel is the presence of chloride
salts in the concrete. In sufficient concentrations, they can undermine the passive
film of the steel locally and bring about pitting corrosion. This is illustrated by a
modified Pourbaix diagram (Fig. 8) and by a series of polarisation scans of steel
in concrete contaminated with chloride (Fig. 9). It is evident from Figure 9 that the
corrosion potential becomes more negative and the corrosion rate increases as
the chloride concentration increases.

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Potential (NHE Scale), V
1

General Corrosion Pitting

0 Imperfect Passivity
Perfect Passivity

-1 Corrosion
Immunity

0 2 4 6 8 10 12 14
pH

Figure 8 Modified Pourbaix diagram for steel in solutions

contaminated with chloride

Pitting
Potential
Potential (E)

Increasing
Chloride

Current (i)

Figure 9 Evans diagram for steel undergoing pitting corrosion in

chloride contaminated concrete

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Durability assessment and corrosion detection of steel reinforcement
There are a few obvious and simple techniques that should be carried out initially
in order to obtain an overall picture of the condition of the reinforced structure. A
good visual survey is probably the most important step in the assessment. It is
essential to visit the site and look for tell-tale signs such as cracking of the
concrete, rust staining, delamination but perhaps more importantly, signs of water
retention, inadequate drainage and, particularly in flat surfaces such as car parks,
formation of paddles. Edges and crevices should be studied carefully. An
assessment of possible environmental factors such as exposure of structure to
direct rainfall, sun and wind should be made. Then, key regions that may require
detailed investigation can be selected.

Chloride and carbonation survey

As was discussed earlier, both carbonation and chloride infestation can lead to
corrosion of the reinforcement. If chlorides are suspected, dust samples should
be collected from selected nodes on a grid at increasing depths into the concrete.
This can be done simply with the use of a drill. A concentration gradient of
chloride would suggest that the source was external (deicing salts, seawater)
whereas a fairly constant concentration may suggest that the chlorides were
added to the concrete at the mixing stage. The depth of carbonation
(neutralisation of concrete alkalinity by acidic gasses such as CO 2 ) can be
determined by spraying phenolphthalein indicator either on freshly broken
concrete or on drilled powder at increasing depths.

Potential mapping
It was shown above that the potential of steel reinforcement can give a good
indication of its condition. Potential mapping is used, therefore, as a major
investigative technique for the detection of steel reinforcement corrosion. The
set-up for carrying out a potential map is simple and it involves a few easy steps.
First of all, electrical continuity of the reinforcement is checked by measuring the
resistance between two points where the steel has been exposed. A resistance

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of less than 1Ω would normally signify continuity of the steel. The potential on the
steel is then measured relative to a standard reference electrode (normally
copper/copper sulphate or silver/silver chloride) by resting the reference
electrode on the appropriate position on the surface of the concrete as shown in
Figure 10. A potential map can then be constructed (Figure 11) which can show
equipotential contours on the surface of the concrete. Regions of high corrosion
activity can normally be identified as they show characteristically low potentials.

High impedance
voltmeter

Reference
electrode
Sponge (high Electrical
conductivity) connection to steel

Steel Reinforcement Concrete

Figure 10 Simple potential mapping set-up

Half-Cell A0.0
Potentials (mV) A0.5
B0.0
B0.5
Grid (m)

-100-0 C0.0
-200--100 C0.5
-300--200 C1.0
-400--300
D0.0
-500--400
D0.5
D1.0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
Grid (m)

Figure 11 Potential map of concrete section showing several areas of low

potential / high corrosion activity

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It is generally assumed that the probability of corrosion of the steel reinforcement
increases as the potential diminishes. There is, however, a lot of uncertainty in
the middle range of potentials (-200 to -350mV). The problem arises primarily
from the way the potential of the steel reinforcement is determined in practice.
Figure 12 shows diagrammatically the current distribution around a corroding site
(the anode) through the surrounding concrete to the adjacent cathode regions.
These constant current flux lines, give rise to equipotential lines distributed
through the concrete as shown in Figure 12. In a region above the anode the
"apparent" potential is Ea (Fig. 12) and at some distance away at the cathode it is
Ec. The value of Ea is normally less (more -ve) than that of Ec so local corrosion
sites can be identified. It can be seen, however, that the potential measured on
the surface is not necessarily that of the anode. This "surface" potential is
influenced by parameters such as the concrete cover depth and the resistivity of
the concrete which can alter the constant current flux lines and subsequently the
equipotential lines. Wetting of the concrete will inevitably reduce the resistivity of
the concrete and therefore change significantly the potential characteristics.

Equipotential Lines Ea < Ec

Ec Ea Ec

Constant
current flux
lines

Cathode Anode Cathode

Steel

Figure 12 Current and potential distribution in concrete near anodic corrosion

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A further complication which gives rise to a common misunderstanding, is the
fact that steel embedded in submerged or waterlogged structures can exhibit
potentials which are more negative than -0.35 V (CSE scale) whilst suffering
negligible corrosion. This is caused by the inability of oxygen to penetrate the
cover depth in sufficient quantities which leads to the polarisation of the cathodic
reaction as shown in Figure 13.

Provided the condition of the concrete is taken into account, potential mapping,
when used on its own, can provide a reasonable assessment of the corrosion
activity of the reinforcement at the time of the survey. It cannot, however, provide
information on the rate or extent of corrosion.

Figure 13 Evans diagram for passive steel in uncontaminated concrete

containing different concentrations of oxygen

Resistivity measurements
As was shown earlier (see for example Fig. 5), the resistance of the cover
concrete can have a significant effect on the corrosion rate of the reinforcement.
The rate of corrosion at the anode is dependent on the ease with which ions can
pass through the concrete pore electrolyte between the cathode and anode.
Hence a large potential gradient between the anode and cathode associated with

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a low concrete resistivity will normally signify a high corrosion rate of the
reinforcement.

The 4-point Wenner technique, developed from its use in geotechnical surveying,
is a technique that can measure the resistivity of concrete. It involves passing an
alternating current between the outer pair of four equispaced probes in contact
with the concrete surface, as shown in Figure 14. The resistivity of the concrete
can be calculated from the measured voltage between the inner probes from:

ρ = 2π a V
I

Where, a, is the spacing between the probes.

Figure 14 Wenner 4-point probe resistivity measurement.

The resistivity of the concrete will normally be affected by many factors including
moisture and salt content of the concrete, mix proportions, water /.cement ratio,
type of cement replacement etc. As a general rule, if the resistivity of the
concrete is lower than 10,000 Ωcm, the corrosion rate of the reinforcement which
is suspected from a potential mapping survey to be corroding, is likely to be high.
Higher resistivity values would normally signify a lower corrosion risk.

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In theory, it should be possible to estimate fairly accurately with the use of
computer modelling the corrosion current of steel reinforcement from a
combination of potential mapping and resistivity measurements. In practice, there
are, however, limitations as to the accuracy of the obtained potential values, as
was shown earlier, and of the resistivity values owing to the inhomogeneity of
concrete. Increasing the spacing between the probes will diminish the effects of
localised non homogeneity but there is a limit determined by the concrete cover
depth as the highly conductive steel provides an easy path for the input current.
Furthermore, resistivity on the surface layer of the concrete is different to that of
the bulk owing to curing effects, differential wetting or drying and particularly
carbonation of the surface layer. It is common practice to drill shallow holes at the
positions where the probes will be located so that these surface effects are
minimised.

Linear polarisation techniques

The actual corrosion rate of a section of steel reinforcement can be determined
by linear polarisation. The technique essentially involves shifting the corrosion
potential of a known area of steel reinforcement in either the positive or negative
direction with the use of a potentiostat and measuring the current that flows
between the steel and an external auxiliary electrode placed in close proximity to
the steel and in contact with the concrete via the potentiostat. This can be done
in single steps of potential shifts or by scanning the potential over a range of
typically ± 20mV with respect to the corrosion potential. 8 The increase in current
at such a small shift in potential is essentially linear and the gradient of the
current- potential plot gives the polarisation resistance, Rp, which can be related
to the corrosion rate by the Stern and Geary equation:

where βa and βc are the anodic and cathodic Tafel slopes respectively. The
slopes can be determined experimentally but they are normally assumed to be

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about 120 mV/decade so that the above equation is simplified to:

R p = 26 / Icorr

As the corrosion rate can vary by several orders of magnitude such an

assumption is acceptable and will only introduce comparatively small errors in the
calculated corrosion rates. Laboratory work has shown that corrosion rates of
steel in concrete calculated in this way are in good agreement with weight loss
determinations of the same steel. 9

The biggest limitation of this technique is the inherent difficulty of applying it to

large structures where the steel reinforcement cage is electrically connected and
the true area of the steel being polarised during the test is difficult to establish.
Recent developments 10 have attempted to concentrate the polarisation over a
small calculated area of the steel reinforcement with the use of a special anode
arrangement (Figure 15) but problems are always likely to exist because of
variations in the concrete cover depths, the geometry of the structure and the
distribution of the steel reinforcement bars.

Guard Ring Linear Polarisation

Defines Area of Measurement
Digital
Control Half Cell

Counter Electrode

Guard
Ring Anode

-
Steel

- Concrete

Figure 15 Arrangement of insitu linear polarisation device

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Final assessment
A combination of the assessment techniques described above, should give a fair
indication of the present condition of the reinforcement. They do not, however,
show how the corrosion varies with the change of environmental conditions. That
information can be obtained by frequent visits to the site or by continuous
monitoring with the use of embeddable reference electrodes and other probes.
Neither do they reveal the extent of the corrosion and the length of time that
corrosion had been occurring. Figure 16 describes the different stages of the
corrosion process. There is a virtually corrosion-free period before initiation
occurs (a), followed by a period of corrosion propagation (a-b) before the
reinforced structure totally loses its serviceability. A survey of the kind described
earlier can easily detect whether you lie either before or after point a of the graph.
Determining exactly where you are on the propagation stage is much more
difficult and would require exposure of the reinforcement and a detailed structural
assessment.

Acceptable limit
b
Level of corrosion

a
Initiation Propagation

Time

Figure 16 Stages of structural element deterioration related to

reinforcement corrosion

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If the correct choice of assessment techniques is made, the limitations of the
techniques employed are well understood and the results are interpreted wisely,
it is possible to determine whether the structure is sound or whether some
remedial measures are required. The assessment should also assist in the
choice of rehabilitation techniques but that is practically a different discipline.

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References

1. Barneyback R. S. & Diamond S, “Expression and analysis of pore fluid from

hardened cement pastes and mortars", Cem. &Concr. Res. 11, 1981, 279-285.

2. Arup H “The mechanisms of the protection of steel by concrete", Crane A. P.

(ed), 'Corrosion of Reinforcement in Concrete Construction', Ellis Horwood,
Chichester, 151-157, 1983.

3. Gonzalez A., Algaba S. & Andrade C. 'Corrosion of reinforcing bars in

carbonated concrete" Br. Corros. J.,15, 1980, 135-139.

4. Hausmann D. A “Steel corrosion in concrete" Mater. Prot. 6, 1967, 19-23.

5. Burstein Q.T. "Passivity and localised corrosion" Shreir L. L., Jarman R. A. &
Burstein G.T, (eds), 'Corrosion', 3rd edn., 1994, 1.118-1.150.

6. Page C. L. & Tteadaway K. W. J. "Aspects of the electrochemistry of steel in

concrete, Nature, 297, 1982, 109-116.

7. Glass G. K., Page C. L. & Short N. R. "Factors affecting the corrosion rate of
steel in carbonated mortars" Corros. Sci., 32, 1991, 1283-1294.

8. Sergi G., Lattey S. & Page C.L. "Influence of surface treatments on corrosion
rates of steel in carbonated concrete" Page C. L., Treadaway K. W. J. &
Bamforth P. B. (eds), 'Corrosion of Reinforcement in Concrete Construction', SCI
/ Elsevier, London, 1990, 409-419.

9. Andrade C. & Gonzalez J. A. "Quantitative measurements of corrosion rate of

reinforcing steels embedded in concrete using polarization resistance
measurements", Werkstoffe und Korrosion 29, 1978, 515-519.

10. Rodriguez J., Ortega L. M., Garcia A. M., Johansson L. & Petterson K. “On-
site corrosion measurements in concrete structures” Construction Repair,
Nov./Dec, 1995, 27-30

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