Concrete Repair, Rehabilitation and Retrofitting II Alexander et al (eds)

2009 Taylor & Francis Group, London, ISBN 978-0-415-46850-3

Critical chloride content in reinforced concrete State of the art

U. Angst & . Vennesland
Faculty of Engineering Science and Technology, Department of Structural Engineering,
Norwegian University of Science and Technology, Trondheim, Norway

ABSTRACT: In the present work, a large number of publications in connection with critical chloride content
in reinforced concrete has been evaluated. The reported results scatter over more than two orders of magnitude
when expressed as total chloride content by cement weight and over three orders of magnitude when expressed
as Cl/OH ratio. This large scatter is partly the result of different definitions and experimental techniques, but
also due to many factors affecting critical chloride content. Dominating influences have been identified as follows: 1) The steel-concrete interface, 2) the pH value of the pore solution and 3) the electrochemical potential
of the steel. Experimental investigation of the issue of critical chloride content is possible in a wide variety of
procedures. At present, there exists no generally accepted or standardized procedure for the determination of
the critical chloride content.

INTRODUCTION

It is well recognized that the presence of chloride

in reinforced concrete can lead to corrosion of the
reinforcement by destroying the passive layer on the
steel surface (Page & Treadaway 1982). While modern standards impose restrictions on the amount of
chloride that may be introduced to the fresh concrete
mix, penetration of chloride into hardened concrete
is nowadays the major cause for pitting corrosion in
concrete structures.
The concept of critical chloride content in reinforced concrete is based on the general agreement
that corrosion in non-carbonated, alkaline concrete
can only start once the chloride content at the steel
surface has reached a certain threshold value. In literature, this value is normally referred to as critical
chloride content or chloride threshold value. The
knowledge of such values is of importance for service life design or service life predictions when pitting
corrosion is the likely failure mechanism. In service
life modeling, chloride threshold values are required
as input parameters. Whereas more and more, sophisticated mathematical models are developed, there is
still a lack of reliable chloride threshold values and
consequently often conservative values are used
(Schiessl & Lay 2005).
A lot of studies have been undertaken in order
to find chloride threshold values in cement based
materials and the reported results scatter over several
orders of magnitude. This large span of results might
be due to several reasons: First, different definitions

for critical chloride content have been used; second,

various techniques to find critical chloride contents
have been applied by different researchers and, last
but not least, critical chloride content is a complex
matter that depends on a variety of influencing factors. Major parameters are the pH of the pore solution, the electrochemical potential of the steel and the
quality of the steel-concrete interface (COST 521).
The inhibiting effect of high pH levels was recognized early (Hausmann 1967, Gouda 1970). Since the
presence of chloride ions at the steel surface modifies
the anodic polarization curve, primarily by shifting
the pitting potential to more negative values, it is evident that the potential of the steel is of importance
with regard to pitting corrosion: Higher chloride
contents can be tolerated for steel with more negative potentials. This was confirmed experimentally:
The chloride threshold was found to be independent
of the potential for values higher than 200 mV vs.
SCE, whereas below that value the chloride threshold increased with decreasing potential (Alonso et al.
2002). With regard to the steel-concrete interface, it
is a dense and lime-rich layer of hydration products
that protects the steel by acting as a physical barrier
and buffering the pH in the pore solution (Page 1975).
Lower chloride threshold values have been reported
when the formation of this layer on the steel surface
was restricted (Yonezawa et al. 1988). It has to be
noted that the condition of the interface cannot be
quantified.
Given the numerous investigations undertaken
on critical chloride content in reinforced concrete,

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literature reviews were published towards the end

of the 1990s (Glass & Buenfeld 1997a, b, Breit
1998b, Alonso et al. 2000). In the present article,
these reviews are brought up to date by including newer publications. The available literature is
evaluated with regard to definitions, techniques
and results.

shows that different chloride threshold values are

obtained by using different definitions. Definition
2 leads to higher values, which is the result of a
longer time passing until the chloride content is
determined.
2.2

2
2.1

DEFINITIONS
Critical chloride content

The critical chloride content can be defined in two

ways (Schiessl & Lay 2005): From a scientific point
of view, critical chloride content is usually defined as
the chloride content required for depassivation of the
steel (definition 1). However, it has to be kept in mind
that depassivation may not necessarily lead to deterioration, e.g. in a dry concrete the corrosion rate is kept
low due to ohmic control of the current flow. Thus,
from a practical, engineering point of view, critical
chloride content is often defined as the chloride content associated with visible or acceptable deterioration of the structure (definition 2). It has to be noted
that the term acceptable deterioration is somewhat
imprecise and confusing.
Figure 1 illustrates these two different definitions by combining Tuuttis corrosion model (Tuutti
1982) with an assumed constant chloride ingress
leading to a linear increase in chloride concentration at the steel reinforcement. The figure clearly

Expression of critical chloride content

The critical chloride content is most commonly

expressed as total chloride content relative to cement
weight. The main reason for this is the fact that the
determination of total chloride content is relatively
simple and well documented in standards. Since the
binder content is not always known, it is sometimes
preferred to relate the total chloride content to the
weight of concrete.
Since only the free chlorides are generally considered to be of importance for corrosion initiation,
the critical chloride content is sometimes expressed
by use of free chloride contents, either related to the
binder or concrete weight or as a concentration in
mol/l in the pore solution.
The form of relating the chloride concentration
to the hydroxide ion concentration, i.e. expressing
critical chloride content as Cl/OH ratio, is based
on work conducted in solutions (Hausmann 1967,
Gouda 1970). It was however noted that the Cl/OH
ratio depends on the pH and increases with higher
pH, i.e. the inhibiting effect of OH is stronger at
higher pH levels (Li & Sags 2001). This form was
considered as the most accurate to express critical
chloride contents, but Glass and Buenfeld argue
that this is not supported by analysis of available
data in literature (Glass & Buenfeld 1997b). They
suggested that presenting critical chloride contents
is best done in the form of total chloride by weight
of binder.
The various forms to express critical chloride
contents reflect both the destructive species and
the inhibitive properties of the concrete in different ways. Table 1 sums up the available expression
forms.

Table 1.
content.

Different forms to express critical chloride

Aggressive species

Inhibitive property

Expressed as

Total chloride

by binder weight
by concrete weight
by binder weight
by concrete weight

% by weight
% by weight
% by weight
% by weight

by OH concentration

mol/l
Cl/OH

Free chloride
Free Cl
Figure 1. Different definitions for critical chloride content
based on Tuuttis model.

312

concentration

3.1

EXPERIMENTAL APPROACH
TO CRITICAL CHLORIDE CONTENT
IN CONCRETE
Test setups

In order to experimentally investigate the issue of

critical chloride contents in reinforced concrete the
experimental setup has to include the following:
1. A steel electrode of interest embedded in a cement
based material (cement paste, mortar, concrete) or
immersed in a solution that simulates the concrete
(synthetic pore solution).
2. Chloride ions present at the steel surface, either at
a constant concentration or increasing over time.
3. Detection of the depassivation of the steel electrode (or acceptable degree of corrosion when
sticking to definition 2).
4. Quantification of the corresponding chloride content at the steel surface.

To achieve a setup that fulfils these four requirements, a lot of possibilities exist. A variety of options
are available only for selecting a steel electrode: Different steel types exist (normal carbon steel, stainless
steel, galvanized steel, etc) in different shapes such
as smooth or ribbed bars and they can be prepared
in several ways, e.g. polished, sandblasted, pre-rusted,
etc. Also with regard to the chlorides, several possibilities are available: The type of chloride salt (NaCl,
CaCl2, etc) and a method by which the chloride is
introduced at the steel surface must be selected. In
case of cement paste, mortar or concrete, chloride
might be added directly to the mix or introduced later
into the hardened material by capillary suction and/
or diffusion or accelerated by migration; in solution
experiments, the dynamic increase of chloride concentration with time is easily done by adding chloride to the solution. Also for point 3, the detection
of depassivation or acceptable degree of corrosion,
several techniques are available. Last but not least,

Figure 2. Experimental possibilities to investigate critical chloride content in reinforced concrete.

313

the chloride content associated with corrosion can be

determined and expressed in different ways. An overview of these experimental possibilities is depicted in
Figure 2. Please note that in the present work, as also
in most of the evaluated literature, it is only focused
on normal carbon steel.
Not surprisingly, the multiplicity of possible test
setups leads to poor comparability of the results. This
has to be kept in mind when evaluating reported critical chloride contents.
3.2

Methods to determine the chloride content

3.2.1 Total chloride content

Usually cores are drilled from hardened samples, cut
in slices of a certain thickness, crushed and powdered
and subsequently analyzed in order to obtain a chloride profile. Normally, the acid soluble chloride content is determined; it is also possible to determine
total chloride contents in powder samples by X-ray
fluorescence spectrometry.
3.2.2 Free chloride content
The determination of the free chloride content is
rather easy in solutions, but becomes more complicated when dealing with paste, mortar or concrete. A
few techniques are known to determine the amount of
chloride freely available in the pore solution.
The most accepted method is the pore solution
expression technique: A solid sample is subjected to
pressure and the expressed pore solution is collected
and analyzed. The method is regarded as accurate and
good reproducibility was reported (Tritthart 1989).
However, the application is limited in case of lower
w/c ratios, coarse aggregate particles or dry specimens. In addition, it has to be kept in mind that this
technique results in average values of the sample
volume under investigation; in case of concentration
gradients, no local values can be determined. It was
also noted that under the pressure, part of the bound
chloride is released and increases the chloride content
in the pore solution (Glass et al. 1996).
Leaching techniques are based on mixing crushed
or ground samples with a solvent and measuring the
amount of chloride passing into solution. A variety of
methods have been investigated using different solvents
such as water, methanol or ethyl alcohol and different procedures with regard to leaching time and temperature (Arya et al. 1987). The amount of extracted
chloride was shown to depend strongly on the selected
procedure. In a later study, it was found that also other
parameters such as cement type or source of chloride
affect the results (Arya 1990). It was concluded that
leaching techniques are not practical for determining
the free chloride content. Castellote et al. suggested
a leaching technique based on an alkaline solvent to

extract the free chloride (Castellote et al. 2001). Good

accuracy was reported in comparison with pore solution expression; however, it has to be noted that rather
high chloride concentration levels were investigated
(>2% total chloride by cement weight).
Another technique to determine the free chloride
content is the use of silver/silver chloride electrodes
embedded in the matrix (Molina 1993, Elsener et al.
2003). The potential of these sensors follows Nernsts
law and depends on the activity of the chloride ions in
the pore solution. With these sensors it is thus possible
to measure the free chloride content non-destructively.

LITERATURE EVALUATION

In the present article, nearly 40 references reporting

critical chloride contents from laboratory or field
studies have been evaluated. Not all the available data
can be presented here due to limited space.
Table 2. Reported chloride threshold values in total
chloride content per weight of binder.

Reference

Cl

Cement type

Reported
value

Richartz 1969
Gouda et al.
1970
Stratfull et al.
1975
Locke et al. 1980
Elsener et al.
1986
Hope et al. 1987
Hansson et al.
1990

A
A

OPC
OPC, GGBS

0.4
1.03.0

various

0.21.4

A
A

OPC
OPC

0.40.8
0.250.5

A
D

OOPC
various cements

0.10.19
0.41.37

Schiessl et al.
1990
Lambert et al.
1991
Thomas 1996
Alonso et al.
2000
Alonso et al.
2002
Castellote et al.
2002
Trejo et al. 2003
Manera et al.
2008
minmax

A/D various cements

0.52.0

A/D OPC, SRPC

1.52.5*

D
A

OPC, FA
OPC

0.20.7
1.243.08*

various cements

0.73

D/M SRPC

0.150.23

M
A

0.020.24
0.62.0

OPC
OPC, SF

0.023.08

A = chloride added to the mix; D/M = chloride introduced

into hardened samples by diffusion/capillary suction (D) or
migration (M); *Steel potential below 200 mV vs. SCE.

314

4.1

Publications reporting total chloride contents

Table 2 shows a selection of published chloride threshold values reported in the form of total chloride content per weight of binder. Generally, a large scatter
was found with results from 0.02 to 3.08% chloride by
binder weight (over two orders of magnitude). Details
about the experimental procedures (according to Figure 2) were evaluated but no systematic trends with
regard to characteristics such as cement type, rebar
type (smooth, ribbed) or chloride introduction method
were identified from the totality of the data. Obviously,
the effect of a single parameter on the critical chloride
content is not pronounced enough to be globally apparent. The only factor that appears to have an overall
effect is the electrochemical potential of the steel: In
many studies, this was higher than 200 mV vs. SCE;
in some publications, no potentials were measured
or reported, but in most cases the described exposure
conditions indicate that the potentials presumably were
in the same range. Only in two references (Lambert
et al. 1991, Alonso et al. 2000) steel potentials below
200 mV vs. SCE were reported. The corresponding
critical chloride contents are on a clearly higher level
than in the majority of the other publications.
4.2

Publications reporting Cl/OH ratios

Figure 3 shows a selection of published chloride

threshold values expressed in the form of Cl/OH
ratios. Also this data presents a high overall scatter,
ranging from 0.03 to 45 and thus over three orders of

magnitude. It is evident from Figure 3 that the values

obtained from studies dealing with mortar or concrete samples scatter much more compared to those
from experiments performed in solutions. In addition, remarkably higher chloride threshold values
were reported when investigating mortar or concrete
specimens in comparison with solution experiments.
This might be explained by the inhibiting effects of
the interface of steel embedded in a cement matrix due
to formation of a Portlandite layer at the steel surface
(Page 1975). This is also apparent from the data by
Yonezawa et al. (1988), where the formation of this
layer at the interface was hindered intentionally. Most
authors have not measured or reported the pH and thus
it is not possible to see an overall effect of the alkalinity on critical chloride content. However, the results of
two studies (Breit 1998a, Li & Sags 2001) show that
the Cl/OH threshold ratio increases with increasing
pH of the pore solution, i.e. it is no constant value.
4.3

Experimental procedures

In Figure 2, the components of possible test setups are

schematically depicted; the numbers given under each
box represent the percentage of studies in which the corresponding component was used. For example, in 31%
of the evaluated references chlorides were admixed
initially, whereas in 69% the chlorides were introduced
later. In only 12% of the studies, steel bars were investigated as-received; in the other studies they were
prepared (sandblasted, polished, etc) or no details were

Figure 3. Reported chloride threshold values expressed as Cl/OH ratios. As the values span a large range, they are divided
into two separate plots with different scaling on the ordinate.

315

given. In only 25% of the studies the use of ribbed steel

was reported. In practice, chloride is usually not present
at the steel surface initially, but penetrates into the
hardened concrete during service life. Also the use of
prepared and smooth steel does not give realistic conditions with regard to the steel-concrete interface. The
results of many studies are thus not practice-related.
5

CONCLUSIONS

From this literature review on critical chloride content, the following conclusions can be drawn:
The results available in literature scatter in a wide
range. The reported values span from 0.02 to 3.08%
total chloride by binder weight and thus over two
orders of magnitude. Published Cl/OH threshold
ratios even range from 0.03 to 45, which is over
three orders of magnitude.
No unique chloride threshold value exists. It
depends on various factors which are interconnected and variable with time. Major parameters
have been identified to be 1) the quality of the
steel-concrete interface, 2) the pH of the pore solution and 3) the electrochemical potential of the
steel. The quality of the steel-concrete interface
depends on compaction (voids) and on the presence of a lime rich layer of hydration products;
however, it cannot be quantified. Other influencing factors are the moisture content in the concrete,
type of cement, w/c ratio, temperature, etc.
Experimental investigation of critical chloride contents can be performed in a wide variety of possible test setups. The multiplicity of parameters
includes rebar type (smooth or ribbed), steel surface condition (polished, sandblasted, etc), matrix
(cement paste, concrete, solutions, etc), chloride
introduction techniques (mixed-in, diffusion, etc),
depassivation detection techniques, etc.
The numerous experimental possibilities lead to poor
comparability of the reported results. At present, no
accepted or standardized procedure for the determination of the critical chloride content exists.
Many used test setups are not practice-related.
Although the steel-concrete interface is recognized
as a major influencing factor, smooth and/or prepared rebars (polished, sandblasted, etc) have been
used in many studies. Also, often chlorides have
been mixed-in.

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