Part II

Mechanisms of Corrosion

Corrosion of Steel in Concrete.

Luca Bertolini, Bernhard Elsener, Pietro Pedeferri, Rob P. Polder
Copyright c 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 3-527-30800-8
4
General Aspects

During hydration of cement a highly alkaline pore solution (pH between 13

and 13.8), principally of sodium and potassium hydroxides, is obtained
(Section 2.1.1). In this environment the thermodynamically stable compounds of
iron are iron oxides and oxyhydroxides. Thus, on ordinary reinforcing steel em-
bedded in alkaline concrete a thin protective oxide film (the passive film) is formed
spontaneously [1–3]. This passive film is only a few nanometres thick and is com-
posed of more or less hydrated iron oxides with varying degree of Fe2‡ and Fe 3‡
[4]. The protective action of the passive film is immune to mechanical damage of
the steel surface. It can, however, be destroyed by carbonation of concrete or by the
presence of chloride ions, the reinforcing steel is then depassivated [5].

4.1
Initiation and Propagation of Corrosion

The service life of reinforced-concrete structures can be divided in two distinct

phases (Figure 4.1). The first phase is the initiation of corrosion, in which the rein-
forcement is passive but phenomena that can lead to loss of passivity, e. g. carbo-
nation or chloride penetration in the concrete cover, take place. The second phase
is propagation of corrosion that begins when the steel is depassivated and finishes
when a limiting state is reached beyond which consequences of corrosion cannot
be further tolerated [6, 7].

4.1.1
Initiation Phase

During the initiation phase aggressive substances (CO2, chlorides) that can depas-
sivate the steel penetrate from the surface into the bulk of the concrete:
x carbonation: beginning at the surface of concrete and moving gradually towards
the inner zones, the alkalinity of concrete may be neutralised by carbon dioxide
from the atmosphere, so that the pH of the pore liquid of the concrete decreases
to a value around 9 where the passive film is no more stable (Chapter 5),

Corrosion of Steel in Concrete.

Luca Bertolini, Bernhard Elsener, Pietro Pedeferri, Rob P. Polder
Copyright c 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 3-527-30800-8
72 4 General Aspects

Figure 4.1 Initiation and propagation periods for corrosion in a reinforced-concrete structure
(Tuutti’s model) [7]

x chloride ions from the environment can penetrate into the concrete and reach the
reinforcement; if their concentration at the surface of the reinforcement reaches
a critical level, the protective layer may be locally destroyed (Chapter 6).

The duration of the initiation phase depends on the cover depth and the penetra-
tion rate of the aggressive agents as well as on the concentration necessary to
depassivate the steel. The influence of concrete cover is obvious and design codes
define cover depths according to the expected environmental class (Chapter 11).
The rate of ingress of the aggressive agents depends on the quality of the concrete
cover (porosity, permeability) and on the microclimatic conditions (wetting, drying)
at the concrete surface. Additional protective measures can be used to prolong the
initiation phase (Chapters 13–15, 20) [8].

4.1.2
Propagation Phase

Breakdown of the protective layer is the necessary prerequisite for the initiation of
corrosion. Once this layer is destroyed, corrosion will occur only if water and oxy-
gen are present on the surface of the reinforcement. The corrosion rate determines
the time it takes to reach the minimally acceptable state of the structure (Figure 4.1)
but it should be borne in mind that this rate can vary considerably depending on
temperature and humidity.
 4.2 Corrosion Rate 73

Carbonation of concrete leads to complete dissolution of the protective layer.

Chlorides, instead cause localized breakdown, unless they are present in very
large amounts. Therefore:
x corrosion induced by carbonation can take place on the whole surface of steel in
contact with carbonated concrete (general corrosion);
x corrosion by chlorides is localized (pitting corrosion), with penetrating attacks of
limited area (pits) surrounded by non-corroded areas. Only when very high levels
of chlorides are present (or the pH decreases) may the passive film be destroyed
over wide areas of the reinforcement and the corrosion will be of a general
nature.
If depassivation due to carbonation or chlorides occurs only on a part of the rein-
forcement, a macrocell can develop between corroding bars and those bars that are
still passive (and connected electrically to the former). This may increase the rate of
attack of the reinforcement that is already corroding (Chapter 8).
In structures affected by electrical fields, DC stray current in the concrete can
enter the reinforcement in some areas (i. e. it passes from the concrete to the
steel) and return to the concrete in a remote site. The passive layer can be de-
stroyed in those areas where the current leaves the steel (Chapter 9).
On high-strength steel used in prestressed concrete (but not with common rein-
forcing steel) under very specific environmental, mechanical loading, metallurgical
and electrochemical conditions, hydrogen embrittlement can occur, which may lead
to brittle fracture of the material (Chapter 10).

4.2
Corrosion Rate

The corrosion rate is usually expressed as the penetration rate and is measured in
mm/y. Often, especially in laboratory tests, it is expressed in electrochemical units,
i. e. in mA/m2 or in mA/cm2. In the case of steel, 1 mA/m2 or 10 mA/cm2 corre-
sponds to a loss of mass equal to approximately 90 g/m2 p y and a penetration
rate of about 11.7 mm/y.
The corrosion rate can be considered negligible if it is below 2 mm/y, low between
2 and 5 mm/y, moderate between 5 and 10 mm/y, intermediate between 10 and
50 mm/y, high between 50 and 100 mm/y and very high for values above 100 mm/y.
Figure 4.2 shows the typical ranges of variation of the corrosion rate in carbonated
or chloride-contaminated concrete as a function of relative humidity (R. H.) of the
environment.
74 4 General Aspects

Figure 4.2 Schematic representation of corrosion rate of steel in different concretes and
exposure conditions (after [9], modified)

4.3
Consequences

The consequences of corrosion of steel reinforcement do not involve only the ser-
viceability or the external condition of the structure, but may also affect its struc-
tural performance, and therefore its safety.

Figure 4.3 Structural consequences of corrosion in reinforced concrete structures [10]

 4.3 Consequences 75

The main consequences of corrosive attack are shown in Figure 4.3. Corrosion is
often indicated by rust spots that appear on the external surface of the concrete, or
by damage to the concrete cover produced by the expansion of the corrosion prod-
ucts. These products in fact occupy a much greater volume than the original steel
bar. The volume of the corrosion products can be from 2 to 6 times greater than
that of iron they are derived from, depending on their composition and the degree
of hydration. For example, the volumes of the oxides Fe3O4, Fe(OH)2, Fe(OH)3,
Fe(OH)3.3H2O are, respectively, 2, 3, 4, and 6 times greater than that of iron. In
general, the volume of the products of corrosion, a mixture of these oxides, can
be considered 3–4 times the volume of iron. Consequently the products of corro-
sion can produce tensile stresses that generate cracks in the concrete cover
(Figure 4.4a), spalling in a localized area, or complete delamination (Figure 4.4b).
Reduction of bond of the reinforcement to the concrete may also occur.

Figure 4.4 Examples of consequences of cor- cross section of the rebar due to pitting corro-
rosion of steel in concrete: a) cracking of col- sion; d) brittle failure of prestressing tendons
umn and cross beam; b) spalling and delami- due to hydrogen embrittlement
nation of the concrete cover; c) reduction of
76 4 General Aspects

In cases of localized corrosion, the cross section of the reinforcement can be

significantly reduced (Figure 4.4c) and thus its loading capacity and its fatigue
strength. Finally, under very special conditions that lead to hydrogen embrittle-
ment of high-strength steel, brittle failure of some types of prestressing steel can
take place (Figure 4.4d).

4.4
Behaviour of Other Metals

The behaviour of metallic materials other than those used as reinforcement should
be briefly mentioned. Zinc, galvanized steel and stainless steels will be dealt with
in Chapter 15.
Aluminium is passive in environments with a pH between 4 and 9, but not in
alkaline media such as the pore solution of non-carbonated concrete. When it
comes in contact with fresh cement paste, aluminium reacts by developing hydro-
gen, sometimes vigorously. Once the concrete has hardened, aluminium and alu-
minium alloys suffer general corrosion; the higher the moisture content of con-
crete, the higher the corrosion rate. In dry concrete the corrosion rate is negligible.
Considerable loss of mass can take place in wet concrete, leading to the production
of voluminous corrosion products that can spall off the concrete cover. The corro-
sion rate tends to decrease in time, since the corrosion products hinder the trans-
port of alkalis to the corroding surface. The mass loss is lower in concrete with
lower pH, and it becomes negligible in carbonated concrete [11]. Lead too corrodes
in alkaline environments. Its initial reactivity is lower than that of aluminium.
However, the attack in humid concrete continues, because the environment pre-
vents the formation of a layer of basic lead carbonate, which is usually present
on the surface of lead exposed to neutral environments (e. g. the atmosphere or
fresh water). Copper and its alloys do not corrode, unless in the presence of ammo-
nia compounds, for instance coming from some admixtures; in this case, phenom-
ena of stress-corrosion cracking can occur. Titanium is perfectly passive in all types
of concrete (with or without chlorides, carbonated or uncarbonated) even at very
oxidising potentials. This is why it is used as a base metal for anodes in cathodic
protection of reinforcement. Nickel and its alloys behave optimally, even in the pres-
ence of chlorides and in carbonated concrete.

References
[1] M. Pourbaix, Lectures on Corrosion,
Plenum Press, New York, 1973.
[2] V. K. Gouda, “Corrosion and corro-
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British Corrosion Journal, 1970, 5,
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[3] H. Arup, “The mechanisms of the
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[4] A. Rossi, G. Puddu, B. Elsener, “The
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[8] C. L. Page, “Corrosion and its Con-
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[11] U. Nürnberger, “Corrosion of metals
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