Cement and Concrete Research 173 (2023) 107287

Contents lists available at ScienceDirect

Cement and Concrete Research

journal homepage: www.elsevier.com/locate/cemconres

Chloride profiles – What do they tell us and how should they be used?
Klaartje De Weerdt a, *, William Wilson b, Alisa Machner c, Fabien Georget d
a
Department of Structural Engineering, Norwegian University of Science and Technology (NTNU), Norway
b
Department of Civil and Building Engineering, Université de Sherbrooke, Sherbrooke, QC, Canada
c
TUM School of Engineering and Design, Technical University of Munich (TUM), Germany
d
Institute of Building Materials Research, RWTH Aachen University, Germany

A R T I C L E I N F O A B S T R A C T

Keywords: Chloride profiles are used to select concrete compositions for new reinforced concrete structures, evaluate the
Chloride condition of existing structures, and to predict their remaining service life, all with regard to chloride-induced
Concrete reinforcement corrosion. They are invaluable tools for improving the sustainability of our infrastructure. We
Corrosion
examine what chloride profiles tell us and how they should be used. Through a series of case studies, we establish
Service life modelling
Diffusion
a list of crucial research questions that provide a direction for future research in this field: What is the contri­
bution of chloride binding to chloride transport? What is the path for chloride transport in concrete? How are our
findings on chloride profiles relevant for reinforcement corrosion? We then discuss the implications of the an­
swers to these questions for engineering and mechanistic modelling practices.

1. Introduction development of new concrete compositions or binders and during the

Chloride-induced corrosion of steel reinforcement is one of the main
degradation mechanisms for reinforced concrete structures worldwide
and is therefore a major threat to our global infrastructure [1]. Ever so
important, the mechanisms of chloride ingress are still not fully
understood.
Although chloride ingress determines the service life of many rein­
forced concrete structures, their design and maintenance rely largely on
experience-based prescriptive rules. There is tremendous pressure to
develop new low-CO2-cements with a variety of compositions and
therefore potentially variable resistance to chloride ingress with regard
to chloride diffusivity and chemical interaction with the hydrated
binders. This intensifies the need for models that can predict the dura­
bility of these new binders. For such models to work accurately, the
fundamental mechanisms of chloride ingress and chloride-concrete
interaction need to be known, quantified, and taken into account in
the models. Moreover, we are now designing structures for much longer
service lives and extending the service lives of existing structures. As we
need to act fast, we can no longer rely on long-term experimental testing.
Instead, we urgently need adequate fundamental models based on
experimental input that can be measured relatively rapidly.
Our understanding of chloride profiles will play a pivotal role in this
development. Chloride profiles are a key engineering tool during the
service life of reinforced concrete structures exposed to external chlo­
rides, such as sea water or de-icing salts. When developing new concrete
compositions or binders, chloride profiles from for example accelerated
laboratory tests are used to compare their chloride ingress resistance.
During the service life, chloride profiles are taken to determine the
condition of a structure and plan potential repairs or determine the
remaining service life.
Fig. 1 shows a typical chloride profile, giving the total chloride
content in mass % of dry concrete as a function of depth from the
exposed surface. Such profiles are determined by obtaining ground
concrete powder at different depths from the exposed surface and ana­
lysing its chloride content. There are a number of international stan­
dards describing this process, e.g., NT BUILD 443 [3], ASTM C1556-11a
[4], and EN 12390–11 [5]. Amongst other things, profiles show the
extent to which chlorides have penetrated the concrete at a certain point
in time. The common purpose of chloride profiles is to get an insight into
to how high the chloride levels are at the reinforcement as a function of
time, and whether these levels can cause corrosion.
The left-hand sketch in Fig. 1 illustrates typical features of a chloride
profile, where a) the height reflects the amount of chloride present in the
concrete at a specific depth; b) the width reflects how far the chlorides
have penetrated into the concrete; and c) the surface phenomena relate
to the peaking of the profile near the surface.

* Corresponding author.
E-mail address: klaartje.d.weerdt@ntnu.no (K. De Weerdt).

https://doi.org/10.1016/j.cemconres.2023.107287
Received 10 March 2023; Received in revised form 10 July 2023; Accepted 24 July 2023
Available online 14 August 2023
0008-8846/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
K. De Weerdt et al.
These features are affected by a number of parameters. This paper
focuses on the impact of two parameters on each of these features: 1) the
exposure conditions, and 2) the binder type. We start with a general
introduction to chloride profiles and then demonstrate the impact of
these parameters by referring to specific case studies. To guide the
reader through the complexity of chloride profiles, we begin with
simplified descriptions and move progressively to more advanced
characterization and modelling.
This paper only considers chloride ingress from an external source, e.
g., sea water or de-icing salts, and it considers the components of the
unexposed concrete to be “chloride-free”. We will focus mainly on
submerged exposure and will not go into drying and wetting or salt
spray exposures. We do this because even in the simple case of
controlled standard bulk diffusion experiments, there are still crucial
knowledge gaps that need to be filled in before we can widen our focus.
The chloride content in the vicinity of the rebar is key with respect to
corrosion. The critical chloride content is a crucial parameter when it
comes to service life modelling. The critical chloride content is an even
more complex topic than chloride ingress, though it will not be the focus
of this paper. We will, however, indicate how the findings presented
here would also impact the critical chloride content.
This is not a review paper. There are very comprehensive textbooks
on chloride ingress available, such as Shi et al. [6], Tang et al. [7], and
Bertolini et al. [8]. Excellent reviews on chloride binding are also
available [9–11].
On the basis of simple calculations and a selection of case studies, the
aim of this paper is to explain our current understanding of chloride
profiles, to highlight the research gaps we have encountered, and to
provide insights into how these profiles can be used for engineering
purposes as well as for fundamental research aimed at elucidating the
mechanisms involved in chloride ingress.
The paper is divided in two main parts: the first focuses on case
studies and the second on modelling. In the first part (Section 2), we start
with a basic explanation of what a chloride profile is followed by a set of
case studies focusing on the impact of exposure and binder type on the
shape of chloride profiles. In the modelling part (Section 3), we discuss
the use of chloride profiles as input or output for both engineering and
mechanistic models.
The paper evolves around the following reoccurring research
questions:
1. What is the contribution of chloride binding to chloride transport?
2. What is the path for chloride transport in concrete?
Fig. 1. Sketch showing the total chloride profiles from a concrete element submerged in sea water at Solsvik field station (Norway) for 16 years. The concrete was
made with a Portland composite cement containing 4 % silica fume and 19 % fly ash [2]. On the left, typical features of the chloride profile are marked with letters.
On the right, the two main causes that affect the shape of chloride profiles are marked with numbers. These main causes will be addressed in this paper by means of
case studies.
2
Cement and Concrete Research 173 (2023) 107287
3. How are our findings on chloride profiles relevant for reinforcement
corrosion?
At the end of the paper, we summarize how our findings on chloride
profiles feed into these questions.
2. Understanding chloride profiles
This section focuses on case studies aimed at understanding chloride
profiles. We start by looking at the basics of chloride profiles for readers
who have not worked with chloride profiles before. In Section 2.2 we
look into the impact of exposure on chloride profiles using two experi­
mental set-ups. Finally in Section 2.3, we discuss the impact of the
binder type.
2.1. Chloride profile basics
Concrete is a composite material consisting of aggregates and sand
held together by cement paste. With respect to chloride resistance,
cement paste is the “active part”, and both aggregates and sand can be
considered “inert”. The total chloride content or “height” of the chloride
profile is therefore largely determined by the binding capacity and
amount of the cement paste in the concrete. Similarly, the chloride
ingress depth or “width” of the profile is a measure of the chloride
penetration resistance of the cement paste, which relates to its porosity
and transport properties. Finally, we need to take into account the
heterogeneity of the concrete, especially near the surface.
2.1.1. Chloride binding and the height of profiles
Chloride profiles represent the total chloride content, comprising
both free and bound chlorides. When hydrated cement paste comes into
contact with a chloride-containing solution, some of the free chlorides
from the liquid phase will become bound. This binding can occur
chemically or physically. Chlorides are chemically bound by their
incorporation into the interlayer of AFm phases [12–17]. In this paper,
we will refer to these phases as Friedel's salt solid solutions (FSss) or
more generally, chloride containing AFm (Cl-AFm). Chlorides can also
accumulate in the diffuse layer of the C-A-S-H. This accumulation is
usually referred to as physical binding [6,18–23]. In this paper, the
abbreviation C-A-S-H is used to refer to calcium aluminosilicate hydrates
(instead of the more traditionally used C-S-H) to take into account the
aluminate content typically observed in hydrated cement paste [24,25].
To understand chloride profiles, we need to know how much of the total
K. De Weerdt et al.
chloride is actually bound, and in which phases it is bound.
To illustrate how much of the total amount of chloride can actually
be bound, we present here a preliminary estimate of the potential
contribution of free and bound chlorides to the total chloride content.
Note that we consider AFm and C-A-S-H to be the main phases respon­
sible for the chloride binding of hydrated cement paste. Other phases,
such as calcium hydroxychloride hydrates [26,27] are not considered
here, and adsorption on surfaces other than C-A-S-H, e.g., portlandite
[28], is considered negligible.
For the estimate, we used the total chloride profile of a PC-FA con­
crete exposed to chlorides for 16 years submerged in sea water [2] as
shown in Fig. 1. We focused on the chloride content measured in sec­
tions between 5 and 10 mm in depth where the total chloride content is
about 0.5 wt% of dry concrete. We focused on this depth as we wanted to
look at a relatively higher chloride content near the exposed surface, and
at the same time avoid the outermost sections (0–5 mm) due to the in­
crease in paste content in the concrete close to the exposed surface,
which is caused by the wall effect and which is further described in
Section 2.1.3.
The supplementary data to this paper gives a detailed description of
how we calculated the amount of free chloride and the amount of
chloride bound in Friedel's salt and C-A-S-H. The results are shown in
Fig. 2. As input data, we used the suction porosity of the concrete of 15
vol% [2], the phase assemblage calculated by thermodynamic modelling
based on the binder composition [2], and an estimated Cl/Ca molar-
ratio for the C-A-S-H of 0.05 [2,29,30].
What this simplified calculation demonstrates is that a large share of
the total chloride content is actually not present as free chlorides, but
instead is taken up by solids (Fig. 2). Therefore, to understand chloride
profiles, we need to understand the interactions between the chlorides
and the hydration phases.
It should be noted that estimating the free chlorides is not easy
because it relies on an estimation of the porosity, which we assume to be
filled with a solution with a chloride concentration similar to sea water
(i.e., 0.5 mol/L). The chloride concentration in the pore solution at a
depth of 10 mm is assumed to be close to the one in the pore solution at
the exposed surface and to decrease when moving deeper into the
concrete. Thus, assuming a similar concentration as in the exposure
solution at 10 mm depth is a simplification and will lead to an over­
estimation of the free chloride content. The value of the porosity is
highly dependent on the method used to measure it [31]. In this case, the
samples were dried at 105 ◦ C to determine the pore volume, which we
assumed to be filled with the same chloride concentration as the expo­
sure solution. The pore volume (and with it the amount of free chloride)
Fig. 2. Left: the predicted phase assemblage of the cement paste in the PC-FA
concrete (w/b = 0.42) exposed for 16 years submerged in sea water [2]. Right:
the distribution of the total chloride content between free chlorides in the pore
solution, chemically bound in the Friedel's salt, and physically bound by the C-
A-S-H. The detailed calculations are given in the supplementary data.
3
Cement and Concrete Research 173 (2023) 107287
can be slightly overestimated due to the loss of some solid phases when
drying at 105 ◦ C. In addition, both the stoichiometry of Cl-AFm and the
composition and chloride content of C-A-S-H can vary greatly, which
affects their contribution to the total chloride content.
Although there are some uncertainties in the example presented, a
similar picture has been obtained in other studies (see Fig. 8 in Section
2.2 and Fig. 11 in Section 2.3). The general idea of Fig. 2 should
therefore be kept in mind. We discuss this in more detail with respect to
the exposure conditions (Section 2.2) and the binder type (Section 2.3).
Finally, it is important to note that the cement content in concrete (e.
g., in kg/m3) has a large impact on the potential amount of chloride
bound in the concrete. A concrete with a low cement content of, e.g.,
220 kg/m3, has only half the theoretical potential binding capacity of a
more cement-rich concrete with 440 kg/m3 cement, and this is without
taking into account the shrinkage or potential differences in water-to-
binder (w/b) ratios. So, when the heights of different chloride profiles
are compared, the cement content of the concrete is a crucial parameter.
What can we learn from these findings with respect to the first key
question raised in the introduction - What is the contribution of chloride
binding to chloride transport? We have seen that a major part of the total
chloride content shown in typical chloride profiles is bound in hydrates,
whereas only a minor share is found in the pore solution. Chloride
binding is therefore important for our understanding of chloride pro­
files. Based on the information presented here, we cannot yet say any­
thing on the impact of chloride binding on chloride ingress.
2.1.2. Chloride ingress and the depth of profiles
The chloride ingress resistance of concrete is determined by its pore
volume and, even more importantly, the pore structure of the concrete
or mortar, which in turn means the pore structure of the cement paste
and its interfacial transition zone (ITZ) because the aggregates can be
considered inert. In principle, the chloride ingress resistance for a spe­
cific binder can be governed by adjusting the w/b ratio of the concrete.
This is reflected in regulations and norms when they prescribe a
maximum allowed w/b ratio or a minimum compressive strength range
for a given exposure condition, e.g., EN 1992 [32], EN 206 [33], and
CSA A23.1:19 [34]. According to the Power's theory [35,36], a plain
Portland cement would theoretically require 42 wt% of water to allow
full reaction, assuming 23 % of non-evaporable water content and 19 %
of gel water. With a w/b ratio of 0.42 therefore, the cement matrix
would be filled with hydration products and gel pores, although
contraction pores would form due to chemical shrinkage. With higher
w/b ratios, there is excess water, which results in capillary pores which
can lead to a considerable decrease in the ingress resistance of the paste
if these capillary pores are connected [37–39]. This is why most w/b
ratios for durable chloride-exposed concrete are in the range of
0.45–0.40 or lower, even though cement hydration in concrete is
generally not complete. For more severe exposure conditions, e.g.,
splash or tidal zone vs. airborne chlorides, or where a longer service life
is required, a lower water-to-binder ratio is usually prescribed. Fig. 3
(left) illustrates the impact of varying the w/b ratio in the lower range of
w/b ratios. However, we should keep in mind that a lower w/b ratio
typically results in a higher cement content (in kg/m3) of the concrete in
order to maintain a similar paste volume in the concrete, thereby leading
to a larger initial environmental footprint for the concrete. Thus, from a
life cycle assessment point of view there will be a balance between the
w/b ratio and the cement content or, in other words, between the service
life and the built-in emissions.
Fig. 3 (right) shows how the binder plays a dominant role in the
chloride ingress resistance of concrete. For the same w/b ratio and
binder content, an increase in the silica fume content from 5 to 10 % has
a similar or even better effect than reducing the w/b ratio from 0.40 to
0.25 (Fig. 3, left). Section 2.3 focuses on the impact of the binder type
and discusses how certain composite cements form more favourable
pore structures with higher resistance to chloride ingress and can
therefore either be used at higher water-to-binder ratios than for
K. De Weerdt et al. Cement and Concrete Research 173 (2023) 107287

Fig. 3. Sketches based on data from Tang [40] for chloride profiles from concrete exposed submerged in a marine environment for 5 years. Left: binder consisting of
95 % PC and 5 % silica fume (SF) with varying w/b ratios, i.e.,0.25, 0.30, and 0.40 (H5, H1 and H4 in the reference; with a binder content of 550, 500 and 420 kg/m3
concrete). Right: binders consisting of 95 % PC + 5 % SF and 90 % PC + 10 % SF both with a w/b ratio of 0.30 and a binder content of 500 kg/m3 concrete (H1 and
H2 in the reference). Note that the profile is normalized to the binder content using the amount of calcium in the powdered concrete and the calcium content of
the binder.

example a concrete with plain Portland cement or be used to provide a Moreover, it should be noted that normalization by the calcium content
longer service life. only works with aggregates that do not contain calcium, e.g., granite
How do these observations feed into the second key question raised aggregate [43]. An alternative method that allows normalization of the
in the introduction - What is the path for chloride ingress in concrete? So chloride content to the paste content would be μXRF-scanning, where
far, we have seen that the cement paste part and the ITZ of the concrete applying filters on elemental maps makes it possible to distinguish be­
determine its chloride ingress resistance and that the w/b ratio and tween aggregates and paste, and thereby plot the chloride ingress
binder type affect the pore volume and, more importantly, the pore normalized to the paste content.
structure or pore connectivity in the cement paste and potentially also The type of surface also seems to affect the chloride ingress depth (x)
the ITZ. through another competing mechanism [42]. Concretes with cast sur­
faces show a tendency to have a slightly improved chloride ingress
2.1.3. Units of chloride profiles and surface phenomena resistance compared to sawn surfaces after 5 years of exposure (see
When we discuss and compare chloride profiles, we should pay Fig. 4). Variations in x are below 5 mm for 0.1 wt% Cl per concrete. This
attention to the units used. Chloride content can be expressed as wt% of has been related to the introduction of defects at the surface during
the concrete or normalized to the binder content and expressed as wt% sawing, which should also be considered in combination with the
of the binder. Both approaches have their drawbacks as discussed in this
section.
When we study concrete cores extracted in the field, the chloride-
exposed surface is typically a cast surface, which means there is a
“wall effect”. At and near a cast surface, a higher paste-to-aggregate
ratio is found than in the bulk concrete, because the concrete has been
cast against a mould or formwork or finished by trowelling. This wall
effect causes fluctuations in the aggregate content, which gradually level
out with increasing distance from the cast surface [41]. Because ag­
gregates can be considered inert (see Section 2.1.1), an increase in the
cement paste content close to the surface leads to a local increase in the
potential binding of chlorides when the chloride content is expressed as
wt% of concrete.
De Weerdt et al. [42] investigated the effect of cast and sawn con­
crete surfaces on the chloride ingress resistance of concretes (daggregate
max = 8 mm) prepared with two different Portland cements and a
Portland fly ash cement (20 wt% fly ash) and exposed for up to 5 years in
a marine splash zone. The total chloride content in the outermost section
(0-1 mm) after 5 years of exposure was >30 % higher for the concretes
with a cast surface than for the concretes with a sawn surface. This was
attributed to the higher paste content in this section for the cast surfaces.
We could take this wall effect into account by normalizing the total
chloride content to the binder or paste content. Tang [40] did this by
analysing both the chloride content and the calcium content of the
concrete powder and using the calcium content as a measure for the
Fig. 4. Chloride profiles after 5 years in the tidal zone for two different con­
paste content. However, this is not very reliable for the outermost sec­
crete compositions both with a w/b ratio of 0.45. PC is plain Portland cement
tions of long-term exposed samples because these sections are also and PC-FA is a blended cement containing about 20 wt% fly ash. The dashed
affected by calcium leaching, as pointed out by Fjendbo et al. [43]. line corresponds to a sawn surface and the solid line to a cast surface [42].

4
K. De Weerdt et al.
difference in paste content.
2.1.4. Critical chloride content
The critical chloride content (Ccrit) or chloride threshold value can be
defined as the chloride content required for the depassivation of the steel
[44]. It is a crucial parameter for service life modelling, both when used
for the design of new structures and for the assessment of existing ones.
In such models, the chloride ingress is typically linked to the chloride
content at the reinforcement and thereby to the critical chloride content.
Some of our findings related to chloride profiles are therefore also
relevant for the critical chloride concept, though the initiation of
chloride-induced corrosion entails far more than a chloride content or
concentration at the reinforcement because it strongly depends on the
conditions at the steel-concrete interface as pointed out in several re­
views [45,46].
Like chloride profiles, the critical chloride content can be expressed
in various ways, as summarized in a review by Angst et al. [44]. Ccrit can
be expressed as a total chloride content relative to the concrete mass, or
as the total chloride content relative to the binder mass, where the latter
allows us to compare critical chloride contents in concrete with different
binder contents.
From a more mechanistic point of view, the free chlorides in the pore
solution could be considered responsible for the corrosion onset,
assuming that the bound chlorides are immobilized and do not
contribute to corrosion initiation. The free chlorides can be expressed
relative to the binder or the concrete mass, or they can be expressed as a
concentration in the pore solution. To take into account the passivating
effect of the alkaline pore solution (high pH) on the steel reinforcement,
the critical chloride content is commonly reported as the ratio between
the chloride ions and the hydroxyl concentration or activity, i.e., [Cl− ]/
[OH− ] [44]. This has been regarded as one of the most relevant defi­
nitions for Ccrit. However, determining the pore solution composition in
the vicinity of the reinforcement is very difficult in practice.
This brings us to the third key question raised in the introduction - So
how are our findings on chloride profiles relevant for reinforcement corro­
sion? As for chloride profiles, when we compare critical chloride con­
tents for different concretes, we need to normalize them either to the
cement content or to the hydration product content. We have shown that
a large part of the total chloride content in concrete is adsorbed or bound
and might not contribute to the initiation of corrosion. More knowledge
about chloride binding and its reversibility therefore seems crucial for
our understanding of the critical chloride content. This will be discussed
further in Section 2.3.
2.2. Exposure solution
This section looks at the impact of the exposure solution on chloride
profiles. We present two studies: one where the impact of other ions in
sea water besides chloride was investigated, and the other where the
impact of the alkalinity of the exposure solution on the chloride profile
was investigated. Taken together, these two studies explain the typical
shape of chloride profiles in submerged marine-exposed concrete.
These studies were carried out on mortar samples with sawn sur­
faces, as is common in accelerated laboratory testing. By investigating
sawn surfaces, we eliminate the “wall effect” observed for cast surfaces
as described in Section 2.1.3.
2.2.1. Multi-ion sea water
In the first set-up, chloride profiles in Portland cement mortars
exposed to sea water were compared with the chloride profiles of a
similar set of mortars exposed to a NaCl solution with the same chloride
concentration as in the sea water (see Fig. 7). The aim was to investigate
whether other ions present in sea water besides chloride would change
the shape of the chloride profile.
5
Cement and Concrete Research 173 (2023) 107287
2.2.1.1. Phase changes and chloride binding. Sea water is a multi-ion
solution. Table 1 shows the main elements present in sea water from
the Trondheim fjord, which has a very similar composition to the
Atlantic Ocean. The presence of these different ions leads to a typical
elemental zonation in the outermost millimetres of marine-exposed
concrete [2,29,30]. Elemental zonation is the formation of zones or
layers parallel to the surface which are enriched in specific ions (see
Fig. 5). From the surface inwards, we observe first a calcite and brucite
crust on the surface and in cracks, followed by a magnesium- and
carbonate-enriched zone where magnesium silicate hydrate (M-S-H) and
calcite can be found; next comes a sulphate-rich zone in which ettringite
is typically observed in voids (e.g., air voids, ITZ, and Hadley grains);
and finally there is a chloride-enriched zone in which Cl-AFm and
chlorides in the C-A-S-H are found [2,29,30].
Fig. 6 shows the predicted changes in the phase assemblage of
Portland cement paste upon exposure to increasing amounts of NaCl
solution (left) and sea water (right) [49]. The phases predicted for sea
water exposure (Fig. 6 right) agree well with the zonation sketched in
Fig. 5. The exposure to increasing amounts of NaCl solution leads to a
decrease in the total volume of the hydration phases, whereas the
changes in the phase assemblage upon exposure to sea water lead to an
increase in the volume of the solids in the cement paste. The volume
increase is caused by the formation of ettringite due to the reaction of
the cement paste with sulphates from the sea water. In addition, the
surface can be covered with a calcite and/or brucite crust.
The elemental zonation at the surface of marine exposed concrete
does not affect the structural integrity of marine structures as it only
affects the outer millimetre of the concrete [2,29,30]. Depending on the
degree of abrasion the surface is exposed to, i.e., currents and particles,
parts of the surface can be abraded away. The magnesium rich phases
are typically observed in cracks and cavities rather than on the surface
when exposed to an abrasive environment, which could indicate that
they form a slightly weaker zone. The sulphate enriched zone in the
investigated concretes in [2,29,30] did not show signs of deterioration
associated with sulphate attack.
2.2.1.2. Chloride ingress. The experimental and modelling results
shown above for sea water indicate a filling of pores, so less chloride
ingress might be expected in the sea water-exposed mortars than in the
NaCl-exposed samples. To investigate how the chloride ingress profiles
are affected by these phase changes in the outermost sections, Portland
cement mortar samples (w/b = 0.40) were exposed by unidirectional
diffusion for 180 days to NaCl solution and sea water with the same
chloride concentration (approx. 0.55 mol/L), which was renewed every
week [49]. Fig. 7 shows the chloride profiles after 21, 90 and 180 days of
exposure to each solution. The portlandite (CH) profiles were deter­
mined using thermogravimetric analysis on the same profile ground
sections as used for the chloride analysis. The loss of portlandite was
used as a measure of leaching because Portlandite is one of the first
hydration phases to dissolve upon leaching (see Fig. 6).
Contrary to what might be expected, chlorides actually penetrated
slightly further for sea water exposure than for NaCl exposure; the
chloride profiles for NaCl exposure lie consistently slightly to the left of
the profiles for sea water exposure. In addition, slightly higher
maximum chloride contents were measured for sea water exposure than
for NaCl exposure.
This means that the filling of (seemingly coarse) porosity by phases
formed due to the additional ions in sea water, such as ettringite, brucite
and calcite, does not necessarily limit chloride ingress. This is relevant
input for the second research question - What is the path for chloride
transport in concrete? It indicates that a reduction in porosity is not suf­
ficient to reduce chloride transport. This makes it even more important
to gain a better understanding of the pore network, and not just the
capillary pores, but also the porosity within the hydrates (i.e., C-A-S-H).
These results also show that NaCl solution can be used to simulate
K. De Weerdt et al. Cement and Concrete Research 173 (2023) 107287

Table 1
Concentrations of the main elements in sea water from the Trondheim fjord [29], standard sea water [48], and the pore solution of Portland cement (PC) paste
containing 5 % limestone hydrated sealed for 140 days [47], all in [mmol/L].
Ca Cl K Mg Na S C pH Ref.

Sea water Trondheim Fjord 8.8 548 8.9 47 411 26.9 0.2 n.d. [29]
Standard sea water 10.5 566 10.6 55 485 29.3 1.9 7.7 [48]
Pore solution PC paste 1.2 n.d. 532 n.d. 279 27.6 n.d. 13.7 [47]

n.d. = not determined.

related to the difference in their intrinsic or ion-specific diffusion coef­

ficient [51] as well as charged-surface effects [52,53]. The slightly
higher total chloride content and deeper ingress measured upon expo­
sure to sea water than in NaCl exposure might be due to the slightly
higher leaching potential of sea water [54], which is supported by the
slightly lower levels of portlandite near the surface in the case of sea
water, as shown in Fig. 7 (right).
All in all, we can conclude that the predicted increase in the volume
of reaction products near the exposed surface upon sea water exposure
does not seem to have a major influence on the chloride ingress.
Nevertheless, chloride ingress seems to go hand in hand with leaching of
hydroxyl ions. This gave Machner et al. [50,55] the idea of the second
experimental set-up, which is presented below.

2.2.2. Effect of leaching

Fig. 5. Sketch illustrating zonation in sea water-exposed concrete showing the
typical phases observed in the respective zones [2,29,30].
chloride ingress from sea water in laboratory experiments, as recom­
mended in current standards, for example EN 12390–11 [5].
When we compare the portlandite profiles with the chloride profiles
in Fig. 7, we observe an inverse relationship between the portlandite
content and the chloride content. This indicates that chloride ingress
goes hand in hand with hydroxyl and calcium leaching and therefore the
dissolution of portlandite. This also agrees with the observation that
sodium does not follow chloride equimolarly into the concrete upon
chloride ingress [2,29,30,49,50]. The difference in the observed
mobility of chloride and hydroxyl ions compared to sodium ions is
We came to the hypothesis that leaching has an important impact on
the appearance of total chloride profiles in concrete. This hypothesis is
supported not only by the dominant impact of the pH and the calcium
concentration on chloride binding demonstrated by Hemstad et al. [56],
but also by the fact that exposure to sea water or NaCl does not seem to
cause sodium ions to follow the chlorides into the concrete [2,29,30],
which indicates that chloride ingress has to go hand in hand with hy­
droxyl leaching to maintain electroneutrality.
To demonstrate the impact of leaching on the shape of total chloride
profiles, mortars were exposed to unidirectional bulk diffusion in a NaCl
solution and in a NaCl solution with KOH (150 mmol/L), referred to here
as NaCl+KOH, both with the same chloride concentration (0.55 mol/L).
The experiments were performed on two sets of mortars prepared with
two different composite cements. The first set of mortars was prepared
with a CEM II/C-M(S-LL) cement containing 50 wt% Portland cement,
40 wt% ground granulated blast-furnace slag, and 10 wt% limestone
filler [55], and the second set with a CEM VI (S–V) cement containing
47 wt% Portland cement, 43 wt% ground granulated blast furnace slag,
and 10 wt% fly ash [50]. Similar results were found in both sets, but in
this paper, we focus on this second set of mortars. The reason KOH was
added to one of the exposure solutions was to limit leaching. The extent

Fig. 6. Predicted volume of phases in Portland cement paste exposed to increasing amounts of NaCl solution (left) or sea water (right) in cm3/100 g cement [49].

6
K. De Weerdt et al. Cement and Concrete Research 173 (2023) 107287

1.2 5

CH [wt.% of dry mortar]

Cl [wt.% of dry mortar]
4
0.9

3
0.6
N_21d
2 S_21d
N_90d
0.3 S_90d
1
N_180d
S_180d
0.0 0
0 5 10 15 0 5 10 15
depth [mm] depth [mm]
Fig. 7. Total chloride profiles (left) and portlandite (CH) profiles (right) of Portland cement mortar exposed in the laboratory to sea water (S) or 0.55 mol/L NaCl
solution (N) for 21, 90 and 180 days, expressed as wt% of mortar dried at 105 ◦ C [49].

of the leaching was investigated by measuring the portlandite content in
the samples as a function of depth from the exposed surface.
2.2.2.1. Phase changes and chloride binding. Fig. 8 shows the chloride
(Cl) and portlandite (CH) profiles of the mortars exposed for 180 days to
NaCl and NaCl+KOH solutions [50]. The mortar exposed to NaCl+KOH
had a reduced portlandite content only in the outermost sections (0–3
mm), whereas the NaCl-exposed mortar showed a decrease in por­
tlandite content up to depths of 10 mm, which confirmed that the KOH
addition was able to limit calcium leaching from the mortar into the
exposure solution.
Moreover, the chloride profiles are dramatically different for the two
exposure conditions. Upon enhanced leaching due to exposure to NaCl,
the total chloride content is three times higher than in the case of
exposure to NaCl+KOH. Since in both cases the mortar is exposed to the
same chloride loading, the difference in the maximum total chloride
content of the exposed samples demonstrates that the chloride load is
not the only factor involved in the results.
To shed light on the changes in chloride binding between the NaCl
and NaCl+KOH exposure conditions, the changes in the phase assem­
blage of the mortars were investigated. Fig. 8 shows the distribution of
the chloride between the pore solution, Friedel's salt, and C-A-S-H. These
proportions were calculated based on the amount of C-A-S-H and AFm
predicted by thermodynamic modelling and their actual chloride con­
tent (Cl/Si and Cl/Al) as determined by SEM-EDS [50]. We can see that
leaching in the NaCl-exposed sample leads to more chloride binding in
both the C-A-S-H and AFm than in the sample exposed to NaCl+KOH.
The impact of progressive leaching on chloride binding in cement
paste was also investigated by Machner et al. [57] and Hemstad et al.
[56], who confirmed that moderate leaching leads to an increase in
chloride binding due to an enhanced chemical and physical binding,
whereas severe leaching (pH <12) leads to a decomposition of the
binding phases and a drop in the binding capacity of the cement paste, as
sketched in Fig. 9. Hemstad et al. [56] related the increase in chloride
binding when the pH drops from 13 to about 12 to an increase in the Cl/
Ca ratio of the AFm solid solution and an increase in the amount of AFm
formed. When the pH drops further, the amount of AFm decreases due to
dissolution, which leads to a reduction in binding. But changes in the
AFm alone only explain part of the pH dependence of the binding
(Fig. 9), which indicates that the C-A-S-H has a similar pH-dependent
behaviour. We calculated the pH dependent chloride uptake in C-A-S-
H by assuming that the difference between the total amount of bound
chloride and the chlorides bound in AFm, are chlorides physically bound
in C-A-S-H (Fig. 9). The increase in chloride adsorption on C-A-S-H with

Fig. 8. Chloride and portlandite profiles for mortars exposed for 180 days to NaCl solution (left) and NaCl+KOH solution (right). The total chloride content is
distributed between the pore solution, Friedel's salt, and C-A-S-H based on thermodynamic modelling and SEM-EDS to determine the actual chloride content in the
Friedel's salt and C-A-S-H [50]. The three zones discussed in the text are indicated with Roman numerals at the top of the graphs.

7
K. De Weerdt et al.
Fig. 9. Left: sketch illustrating the pH dependency of chloride binding (total Cl and Cl in AFm and C-A-S-H) [56,62]; Right: sketch illustrating how leaching can result
in a linear chloride binding isotherm [61].
decreasing pH has been attributed to the increasing calcium concen­
tration in the pore solution, which results in more calcium in the Stern
layer of the C-A-S-H surface rendering it more positive, allowing the
accumulation of more negatively charged chlorides in the diffuse layer
of the C-A-S-H [6,18–23,58–60]. At around pH 12 the chloride in C-A-S-
H starts to decrease as the system's portlandite buffer is consumed,
calcium concentrations decrease, and C-A-S-H starts to decalcify
[56,62]. Note that the contributions of C-A-S-H and AFm to this pH
dependent binding behaviour will be dependent on the phase assem­
blage and thereby the cement type (Section 2.3).
Georget et al. [61] proposed engineering models to describe a pH-
dependent binding isotherm (see Fig. 9, right). Binding isotherms are
typically described as Freundlich or Langmuir functions which are valid
for a specific pH of the exposure solution. By taking leaching into ac­
count, they can turn into a near-linear isotherm. For example, the
outermost section of a marine-exposed concrete which is exposed to the
highest chloride level (in this case 0.5 M) would also be exposed to the
highest level of leaching and therefore the lowest pH. The extent of
leaching decreases with increasing depth below the surface, so the pH
increases and the chloride content in the concrete decreases. The dashed
arrows in Fig. 9 (right) illustrate the movement to higher pH isotherms
with increasing depth in the concrete resulting in an approximately
linear isotherm. This has an important impact when chloride profiles are
used for chloride ingress modelling over time, see Section 3.1.
To put this is in perspective of our third research question - How are
our findings on chloride profiles relevant for reinforcement corrosion? We
have shown that chloride ingress goes hand in hand with hydroxyl
leaching. As described in Section 2.1.4, one of the preferred ways of
expressing the critical chloride content is the [Cl− ]/[OH− ] ratio. This
parameter is affected both by the ingress of chlorides, the numerator,
and by leaching, which decreases the denominator. From a corrosion
initiation point of view, this means we must not only take chloride
ingress into account, but also leaching.
2.2.2.2. Chloride ingress. In addition to changes in the chloride binding
due to various leaching conditions, Fig. 8 also shows differences be­
tween the two exposure scenarios in the chloride ingress depth. Due to
the enhanced leaching upon exposure to the NaCl solution, the chlorides
seem to have penetrated deeper into the concrete than with exposure to
NaCl+KOH. This can be explained by the need to maintain the elec­
troneutrality of the sample, as described by the Nernst-Planck equation
[7]. Consequently, the leaching of ions from the pore solution of a
sample into the exposure solution directly affects the extent to which
other ions are able to penetrate the sample. This is because the charge
8
Cement and Concrete Research 173 (2023) 107287
and number of ions leaving the sample must equal the charge and
number of ions entering it. Limiting the leaching of hydroxyl anions
from the sample [50,55] also limits the ingress of chloride anions into
the sample. So, to fully understand the impact of leaching and ion bal­
ances in the sample on the chloride ingress rate and depth, we need
multi-ion physical transport models that take leaching into account. We
discuss these in the modelling section (see Section 3.2.2).
How do these findings relate to the second research question - What is
the path of the chloride transport in concrete? They indicate that the path of
the chlorides is influenced by the mobility of other ions and the need of
the system to maintain charge balance. Chlorides move into the con­
crete, but cations (e.g., Na+) do not equimolarly follow it into the con­
crete. Instead, we observe that chloride ingress goes hand in hand with
leaching. The charge balance is maintained by hydroxyl ions (OH− )
leaving the concrete as chloride ions enter (Cl− ).
2.2.2.3. Peaking behaviour near the surface. Chloride profiles of long-
term chloride-exposed samples generally exhibit a low chloride con­
tent at the surface followed by the maximum chloride content (a peak or
even a plateau). With increasing depth below the exposed surface, a
gradual decrease in chloride content is observed. We refer to this as
“peaking behaviour”. It can be seen in all the chloride profiles shown so
far (see Figs. 1, 7, and 8).
For chloride profiles determined on concrete with cast outer surfaces
(e.g., Fig. 1), this peaking behaviour contradicts what would be ex­
pected, namely an increase in the total chloride content when
approaching the exposed surface due to an increase in the paste content
as a result of the wall effect (see Section 2.1.3).
For concretes exposed to sea water or road salt spraying, or to the
splash or tidal zone, the peaking behaviour has been attributed to drying
and wetting, which leads to an accumulation of chlorides and other ions
a few mm below the exposed surface [63]. This is a plausible mechanism
for these kinds of exposures, but peaking behaviour is also generally
observed for permanently submerged concrete or mortar, where we
attribute it to the varying degrees of leaching near the exposed surface.
The following three zones can be distinguished (see Fig. 8):
– Zone I is the outermost zone which is heavily leached, leading to the
decomposition of AFm and AFt and the decalcification of the C-A-S-H
causing a dramatic reduction in chloride binding. In the case of sea
water exposure, this zone is enriched in carbonates, magnesium,
potentially sodium, and sulphates.
– Zone II is the moderately leached zone, where leaching leads to a
moderate reduction in pH and therefore enhanced chloride binding
K. De Weerdt et al.
in the C-A-S-H and AFm. This zone comprises the maximum of the
chloride profile.
– Zone III is the zone unaffected by leaching.
It should be noted that Zone I, the heavily leached zone, is only a
couple of 100 μm thick, whereas a typical minimum thickness for a
profile-ground section for a chloride profile is 1 mm. The ground section
of 0–1 mm from the exposed surface thus comprises the heavily leached
Zone I, in which the chloride content is close to zero, but also the
beginning of Zone 2 in which the chloride content increases
[2,30,49,56]. This means that in a conventional chloride profile the very
low chloride content at the surface is not observed, and instead a
reduction in the chloride content is observed in the outer section.
Changes in the value and location of the maximum chloride con­
centration over time due to leaching has an important impact on the
prediction of chloride ingress using analytical models based on the error
function solution of Fick's 2nd law. We come back to this in Section 3.1.
These observations give some insight into the first research question -
What is the contribution of chloride binding to chloride transport? As we
have seen, the total chloride content at the exposed surface can be rather
low and does not reflect the ingress potential, but instead is greatly
affected by leaching. Moderate leaching (pH > 12.4) can lead to
enhanced binding, whereas severe leaching (pH < 10.5) leads to a
decrease in the chloride-binding capacity of the paste. These findings
indicate that chloride binding has a complex impact on the chloride
ingress, depending on the degree of leaching, it might first function as a
sink by accumulating chlorides in hydrates, but eventually it might
function as a source by releasing the chlorides again upon severe
leaching. Nevertheless, chloride binding has an important function in
detecting how far the chloride ions have penetrated into the concrete
and helping us understand the shape of the chloride profiles.
2.3. Effect of the binder composition on chloride profiles
The composition of binders affects both the microstructure of con­
crete and its chloride-binding capacity, so we can expect the chloride
profiles to differ in both depth and height for different binders. This
section explores the impact of the binder composition on chloride pro­
files based on laboratory studies of cement pastes [64,65,67,68].
Working in laboratory conditions avoids the macro-scale effects and the
Fig. 10. Chloride profiles in various cement pastes (w/b = 0.4) after exposure to a 0.5 M NaCl solution for 6 months, as measured by μXRF. The dashed line
represents an arbitrary reference chloride intensity of Cr = 200 counts [67].
9
Cement and Concrete Research 173 (2023) 107287
variability of field conditions, making it possible to focus on the effects
of the binder itself. Six types of binders with three water-to-binder ratios
(w/b = 0.3, 0.4 & 0.5) were investigated: an ordinary Portland Cement
(OPC), a white Portland cement (WPC), a slag-Portland cement (CEM
III/A), a 20 wt% fly-ash blend with OPC (20%FA), a limestone-calcined
clay cement with 50 wt% Portland clinker (LC3–50), and a 20 wt% glass
powder blend with OPC (20%GP).
Fig. 10 shows the chloride profiles measured by μXRF after 6 months
of unidirectional bulk diffusion with exposure to a 0.5 M NaCl solution
(w/b = 0.4) [67]. Considerable variation in chloride ingress depth is
visible between the systems, which we will investigate in Section 2.3.2,
but the profiles have very similar maximal intensities near the exposed
surface. In Section 2.3.1, we explore whether these really indicate
similar chloride-binding behaviour in all samples.
2.3.1. Binding in blended cement pastes
Wilson et al. [65] were able to quantify the distribution of chlorides
with equilibrium experiments for four of the six binders profiled in
Fig. 10, as shown in Fig. 11. Leaching has a significant impact on the
binding (see Section 2.2), so chloride binding was investigated with two
exposure conditions: a solution of 0.5 M NaCl (pH ≈ 12.5 after exposure)
and a solution of 0.5 M NaCl with 0.3 M NaOH (pH = 13.0 after expo­
sure). These are sea water-like chloride concentrations, and we should
note that different behaviour may be obtained with exposure to higher
chloride concentrations.
The total chloride content (obtained by dividing the loss of chlorides
in the exposure solution by the mass of the sample) is of the same order
of magnitude for the different binders. In line with previous observa­
tions (Section 2.2.2), preventing leaching with an exposure solution
with a higher pH (13.0) led to lower total chloride content (shaded bars
in Fig. 11). Similarly, the water-soluble chloride content (measured with
a methodology adapted for pastes from the ASTM C1218 [66]) is of the
same order of magnitude for all binders and decreases with increasing
pH. Strongly bound chlorides were defined as the difference between
total and water-soluble chlorides. Nevertheless, the ratio of strongly
bound chlorides over total chlorides differs between binders (e.g., the
ratio for the LC3–50 system is about twice that of the CEM III/A system).
Moreover, we observe the effect of the binder on the distribution of
chlorides between the pore solution, the Friedel's salt solid solution
(FSss), and the C-A-S-H. Chlorides in the pore solution were defined as
K. De Weerdt et al. Cement and Concrete Research 173 (2023) 107287

Fig. 11. Distribution of chlorides in various pastes (w/b = 0.4) after exposure to 0.5 M NaCl at pH = 12.5 (plain coloured bars) and with 0.3 M NaOH addition to
reach pH = 13 (shaded bars) [65].

the free water content of each paste sample (i.e., the difference in weight
between its saturated surface dry condition and after drying by solvent
exchange) multiplied by the concentration of the exposure solution at
equilibrium. The quantity of chlorides depends mainly on the w/b ratio
and only slightly on the binder type. However, the impact of the binder
on chlorides in FSss and on C-A-S-H is more complex, as we will show
below.
2.3.1.1. Impact of the binder on chemical binding in FSss. The use of
alumina-rich supplementary cementitious materials (SCMs) in blended
cement pastes leads to increased available alumina in the system,
resulting in higher incorporation of alumina in the C-A-S-H structure
and in the formation of additional aluminium-containing hydrates.
These include hydrates from the AFm family that can chemically
accommodate various anions (e.g., OH− , SO2− 2−
4 , CO3 Cl ) into the
− land cement containing dolomite has been shown to take up chlorides to
interlayer of stable phases (monosulphate, hydroxy-AFm, hemi­
carboaluminate, monocarboaluminate, Friedel's salt, Kuzel's salt, etc.) or
their solid solutions, as well as ettringite (AFt) at high sulphate
concentrations, hydrotalcite which in the presence of magnesium com­
petes with AFm/AFt for aluminium, Strätlingite with the local depletion
of Portlandite, and so on. Upon exposure to chloride-rich solutions, some
hydrates can either transform into (or provide alumina for the formation
of) Friedel's salt solid solutions (FSss) [12,69]. This all means that the
AFm content in the cementitious system prior to exposure cannot be
directly used to predict the FSss content after exposure to chlorides [70].
This is also shown in Fig. 12a with the strongly bound chlorides as a
function of FSss content. Higher values are obtained for Al-rich binders,
i.e., 20%FA and LC3 systems. Interestingly, this is not the case for the
CEM III/A system, despite its relatively high alumina content. This
behaviour was explained by the higher contents of magnesium and
sulphate, which lead to the increased formation of hydrotalcite and
ettringite, with little alumina left for FSss. Hydrotalcite formed in Port­
a similar extent as FSss [60], but the hydrotalcite/C-A-S-H mix in this
study (i.e., the inner reaction products of slag particles) was found to
bind chlorides similarly or less than the C-A-S-H itself, i.e., significantly

Fig. 12. (a) Strongly bound chlorides (total minus water-soluble chlorides) vs. FSss (measured by XRD-Rietveld with an external standard), (b) comparison of the
stoichiometry of FSss (χ 2Cl) obtained from XRD-Rietveld and SEM-EDS [65]. The filled symbols indicate values for exposure solutions with pH ≈ 12.5, while the
hollow symbols indicate solutions with pH = 13.

10
K. De Weerdt et al.
less than the chemical binding in FSss.
Furthermore, the FSss can vary in stoichiometry depending on the
binder and exposure conditions. This variation can be described using
χ 2Cl, which gives the ratio between the anions in the interlayer of the FSss
(χ 2Cl = 2Cl/Ca), where χ 2Cl = 1 reflects the theoretical Friedel's salt
composition. Monocarboaluminate has previously been considered as
the other endmember of the solid solution (i.e., χ 2Cl = 0) [12,69].
However, hemicarbonate is considered here as the other endmember
following the study by Georget et al. [71] on the incorporation of guest
ions into the hemicarbonate structure.
Fig. 12b shows the stoichiometry χ 2Cl of FSss for the various binders
investigated. The stoichiometry was determined using two recently
developed methods [65,71–73]; one based on XRD-Rietveld performed
on wet samples (i.e., neither stopped nor dried), and the other using
SEM-EDS combined with phase segmentation EDXIA. The two methods
yielded similar results: the FSss generally reached χ 2Cl ≈ 0.5, which is
about half that of the theoretical stoichiometry of Friedel's salt. More­
over, the increase in the pH of the exposure solution leads to lower χ 2Cl
values, which mean less chemical binding under these exposure condi­
tions, notably for the LC3–50 and 20%FA systems. This agrees with our
previous observations in Section 2.2.2.
Finally, the combination of the amount and stoichiometry of FSss
leads to the values of chlorides in FSss shown in Fig. 11. Due to the
different FSss contents and stoichiometry, the chemically bound chlo­
rides are significantly different between systems, with values higher for
the LC3–50 system and lower for the CEM III/A system. Similar findings
were reported by Babaahmadi et al. [70] and Shi et al. [74], who
investigated the effect of SCMs on the amount of chloride in FSss and C-
A-S-H for composite cements containing various amounts of metakaolin
and/or silica fume.
2.3.1.2. Impact of the binder on physical binding in C-A-S-H. The physical
binding of chlorides occurs in the diffuse layer of the C-A-S-H and can
vary significantly depending on the amount of C-A-S-H, its composition,
the other ions in the solution, and the pH [6,18–23,50,56,75,76]. To
calculate the amount of chloride physically bound in C-A-S-H, one needs
to determine the C-A-S-H content, which can be very challenging in
blended cement systems without relying on complex hypotheses (e.g.,
the amount of water in the C-A-S-H, the incorporation of guest ions, the
reaction degree of the SCMs, variable composition, or the reactivity of
SCM particles). Instead of trying to calculate the total C-A-S-H content,
the problem was simplified by using the amount of Si in the C-A-S-H.
This was calculated using GEMS thermodynamic modelling with input
obtained using XRD-Rietveld for quantifying the crystalline phase con­
tents and using the EDXIA framework with quantitative SEM-EDS
hypermaps to obtain the C-A-S-H chemical composition [58,65,73].
Interestingly, the OPC, CEM III/A and LC3–50 systems showed a
relatively similar amount of Si in the C-A-S-H, even though the phase
assemblage and C-A-S-H composition were very different, with Ca/(Si +
Al) ranging between 1.25 for LC3–50 and 1.9 for the white Portland
paste. Due to a high degree of reaction and a lower AFm content, the
WPC paste had a significantly higher content of Si in the C-A-S-H,
meaning more C-A-S-H is available for physical binding of chlorides than
in the other pastes.
The phase segmentation of C-A-S-H from quantitative chemical
mappings [58,73] also provided the Cl/Si ratio of the C-A-S-H after
exposure: relatively similar values of Cl/Si ≈ 0.06 were obtained for the
blended cement pastes, whereas higher values of Cl/Si ≈ 0.10 were
obtained for ordinary and white Portland cement. These results align
with previous observations showing that physical chloride binding is
higher for higher Ca/(Si + Al) values [50,77–80].
Fig. 11 includes chlorides in the C-A-S-H calculated using the amount
of Si in the C-A-S-H and Cl/Si ratios. These chlorides represent the
majority of the total chlorides in the OPC and WPC pastes, but they make
up a much smaller proportion in the CEM III/A and LC3–50 pastes (in the
11
Cement and Concrete Research 173 (2023) 107287
same range as chlorides in porosity). With this in mind, we should
remember that a relatively small fraction of the chloride in C-A-S-H is
irreversibly bound [23,58], and most chlorides are water-soluble, which
brings us back to the first unresolved question - What is the contribution of
chloride binding (the physical binding in the C-A-S-H) on chloride transport?
2.3.2. Chloride ingress in blended cement pastes
Chloride ions penetrate cementitious materials through the solution
in the pores, interacting and reacting with surfaces along the way.
Wilson et al. [64] investigated properties related to chloride transport
for the pastes presented in Section 2.3.1 in terms of porosity, pore
connectivity, pore solution conductivity, bulk electrical conductivity,
and the effective diffusion coefficient (Deff) obtained using the mini-
migration method in a constant migration regime after the exhaustion
of chloride binding.
The characteristics of the pore network can be captured indirectly
with the formation factor defined as F = σ 0 / σ b [81], where σ 0 is the
conductivity of the pore solution and σ b is the bulk electrical conduc­
tivity. Fig. 13a shows that (by far) the highest inverse formation factor
(1/F) is for WPC systems and the lowest is for LC3–50 systems, which
agrees with the measured Deff (and the penetration depths in Fig. 10).
Very similar results were obtained with the pore connectivity parameter
(β = 1 / Fϕ as defined in several papers [82–84]), which takes into ac­
count both the formation factor and the porosity (ϕ, here the free water
content). Note that the pore connectivity parameter and the tortuosity
parameter (defined in different ways [85–93], one of which is the in­
verse of the connectivity parameter) should be interpreted as descriptors
of the porous network. This includes several phenomena and mecha­
nisms, such as the effects of the geometry of the pore network, in­
teractions between ions and surfaces, and errors from conductivity or
porosity measurements, i.e., the unexplained component of the bulk
conductivity once the effects of the pore solution conductivity and the
porosity have been removed.
Fig. 13a shows that no general relationship for all blended cement
systems could be found between the effective diffusion coefficient and
the characteristics of the porous network (the formation factor and the
pore connectivity parameter), which suggests the presence of the non-
negligible effect of another parameter in chloride transport.
As described in Section 2.2.2, electroneutrality and ion exchange are
key in the process of chloride ingress and binding. Systems with a higher
concentration of ions in the pore solution (and therefore a higher
leaching potential) can be expected to have noticeably more chloride
ingress. Pore solution conductivity is a great measure of the ionic
strength of the pore solution. The binder has a very important impact on
the composition of the pore solution (e.g., its alkali and hydroxyl con­
tents) and therefore on its conductivity [94]. Note that the conductivity
decreases with increasing w/b due to dilution. In the pastes investigated,
the pore solution conductivity for the WPC and LC3–50 systems is about
3–5 times lower than that of the OPC, 20%FA and 20%GP systems. At
the same time, the WPC system exhibits the smallest, and the LC3–50
system the largest, chloride ingress depths in Fig. 10. This shows that the
role of the conductivity of the pore solution must be considered in
combination with that of the porous network, e.g., with the bulk elec­
trical resistivity measurement described below, if we want to be able to
correlate it to chloride ingress.
As Fig. 13b shows, a good correlation (R2 = 0.90) was obtained be­
tween the diffusion coefficient from the mini-migration test (in a con­
stant migration regime, after the exhaustion of binding) and the bulk
conductivity (measured instantly without any chlorides) [64]. This
means that the chloride diffusion potential can be rapidly estimated
without chlorides, using a bulk electrical conductivity measurement.
This bulk conductivity depends on the characteristics of the pore
network and the conductivity of the pore solution, so these parameters
are also the most relevant for the diffusion.
How do these findings feed into the first research question - What is
the contribution of chloride binding to chloride transport? The binders
K. De Weerdt et al.
Fig. 13. Diffusion coefficients for blended cement pastes measured with the mini-migration method (a) as a function of bulk electrical conductivity divided by the
pore solution conductivity (the inverse formation factor), and (b) as a function of bulk electrical conductivity [64].
investigated exhibited different distributions of the bound chloride, see
Fig. 11. Nevertheless, Fig. 14 (adapted from a study with the same pastes
to be published by Wilson et al. [68]) illustrates that there is a very
strong correlation between the bulk conductivity at 3 months and the
penetration depth (Cr = 200 counts) for bulk diffusion experiments after
1 year (R2 = 0.97) and 4 years (R2 = 0.92). This strong relationship has
deep implications for the assessment of chloride ingress resistance. It
indicates that chloride ingress resistance is not affected by the differ­
ences in chloride binding of these systems (i.e., proportions of chemical
and physical binding), because the total chloride content is similar for all
systems exposed to 0.5 M NaCl solutions. Chloride ingress resistance
thus appears to be governed by the properties of the porous network and
the ionic strength of the pore solution, which can be together well
characterized with a bulk conductivity measurement.
We need to combine various observations to answer the second
research question - What is the path for chloride transport in concrete? First,
the C-A-S-H is known to hold multiple scales of porosity (see Section
Fig. 14. Sketch of the penetration depth (Cr = 200 counts) for bulk diffusion
experiments after 1 year vs. the bulk conductivity at 3 months (for selected
blended cement pastes and water-to-binder ratios), data to be published by
Wilson et al. [68].
12
Cement and Concrete Research 173 (2023) 107287
3.2.2) and to have a very high specific surface area prone to interactions
with ions in the pore solution, e.g., physical binding. Second, as shown
both in Georget et al. [58] and in Fig. 11, some of the chlorides in the C-
A-S-H are water-soluble (i.e., not strongly bound). Third, although the
number of pastes investigated is small, a greater ingress depth (Fig. 10)
was observed for systems with a higher level of chloride binding in the C-
A-S-H (Fig. 11).
Therefore, even if the C-A-S-H surface interactions can contribute to
reducing the diffusion rate compared to the diffusion in the pore solu­
tion, this does not mean that the movement of physically bound chlo­
rides is stopped, as is the case with FSss where the chlorides are
chemically incorporated into the hydrate structure. Since the porous C-
A-S-H generally represents a large part of the cement paste volume, a
non-negligible portion of chloride ingress could occur through the C-A-
S-H as further described in the Section 3.2.2.
This concept of a contribution to chloride ingress through the C-A-S-
H needs further validation. Nevertheless, it reinforces the importance of
studying chloride binding, not only in terms of total chlorides, but also
in terms of physical and chemical binding so that we can better under­
stand both diffusion and the critical chloride content.
Did we gather new insights with regarding to our third research
question - How does our understanding of chloride profiles affect our un­
derstanding of the critical chloride content? In Section 2.1.4, we stated that
one of the preferred ways of expressing the critical chloride content Ccrit
is the [Cl− ]/[OH− ] ratio. However, this assumes that the bound chlo­
rides are completely removed from the pore solution and do not take
part in the corrosion initiation. Our observations from Section 2.3.1
show that far from being removed from the system, some of the chlorides
adsorbed on the C-A-S-H appear to be mobile. And in Sections 2.2.2 and
2.3.1, we showed that bound chlorides can be released when there are
changes in the pH. So, perhaps we should focus on the total chloride
content instead.
Glass and Buenfeld [95] argued along the same lines that bound
chlorides can contribute to the corrosion risk and that other factors
besides the hydroxyl concentration in the pore solution, such as the
buffer capacity and the steel interface, can influence the inhibitive
properties of concrete. They therefore proposed to express Ccrit in terms
of total chloride content over the mass of the binder, which is a unit
similar to that used for the chloride profiles and is much easier to
measure. Similarly, Sergi and Glass [96] proposed to express Ccrit as the
total chloride content divided by the acid neutralization capacity of the
concrete, which aligns with our observations in Section 2.2.2: the
binding capacity is pH-dependent and can completely vanish at low pH.
Their method is also experimentally more straightforward than
K. De Weerdt et al.
determining the pore solution composition in concrete at the rebar.
With regard to the impact of the SCMs, we showed in Section 2.3.1.2
that the total amount of hydrates can vary significantly between blended
cement systems with relatively high SCM replacement levels because of
the presence of incomplete SCM reactions or fillers leading to a portion
of the paste remaining unreacted and therefore inert to chlorides.
Potentially, this might make normalization of the critical chloride con­
tent to the total amount of hydrates more relevant than normalization to
the total binder content. However, the definition of Ccrit as the total
chloride/neutralization capacity ratio [96] is independent of normali­
zation to either paste or hydrates and might therefore be of greater in­
terest for more complex blended cement systems.
3. Using chloride profiles
In the previous section, we described the features of chloride profiles
and how concrete composition, exposure and binder type can affect
them. We now discuss the use of these profiles, in particular with regard
to models and simulations, for which they can be used as either input or
output. They are input for models used to derive quantitative material
parameters, the most common being the chloride diffusion coefficient.
They are output for models that predict profiles used to assess the state
of the material and the structure, for example to predict the chloride
penetration depth at a certain point in time or for comparison with in-
situ monitoring.
In this section, we distinguish between two types of models: mech­
anistic and engineering. Mechanistic models aim to describe individually
each contributing mechanism. For chloride ingress, they are reactive
transport models in which the diffusion of chloride ions is the main
transport mechanism. Some models take into account the transport of
other ions and/or water. The transport of chloride is coupled to a
chemical model that describes the binding in the solid phases, using
either a binding isotherm or more complex thermodynamic/kinetic
models. For each of these mechanisms, a separate mathematical equa­
tion can be written. Engineering models, in contrast, lump together all the
mechanisms in a single equation. This is achieved using strong as­
sumptions to simplify the problem (e.g., only diffusion, fixed porosity,
no leaching, etc.) and using lump parameters, such as the apparent
diffusion coefficient [97]. Unlike mechanistic models, which often
require complex numerical solvers, engineering models are simplified to
obtain an analytical solution to the problem. Analytical solutions might
seem a strong mathematical requirement, but as long as only diffusion is
considered, a large number of initial and boundary conditions can be
solved analytically [98]. The engineering models should strive to be
physically representative, and thus, they should derive from the mech­
anistic models. However, as detailed in this section, mechanistic models
also have their fair share of limitations. Therefore, engineering models
often rely on empirical and field validation.
3.1. Profile as input: parameter determination
3.1.1. Can chloride profiles be used to fit mechanistic models?
As described above, mechanistic models contain at least two equa­
tions (chloride diffusion and chloride binding) with at least two vari­
ables (free and bound chlorides). Mathematics requires that two pieces
of information are provided to determine the parameters of these
equations. In Section 2, we showed that the chemical model is full of
uncertainties (C-A-S-H amount, C-A-S-H sorption, AFm solid solution,
pH and leaching, and so on). So, if we attempt to fit the diffusion coef­
ficient on the total chloride profile including the uncertain chemical
model, the fitted diffusion coefficient will be highly unreliable. This is
because chloride binding does not modify the overall diffusion profile
shape, as demonstrated by the successful application of engineering
models such as Fick's second law, which only describe diffusion and not
binding (see the next section).
This argument is confirmed by the many reactive transport models,
13
Cement and Concrete Research 173 (2023) 107287
each based on a large number of assumptions for the chemical model
(elements considered, initial phase assemblage, solid solutions, etc.)
[61,99–105]. They all report excellent results when fitted to selected
experimental data. This is especially true when the calibration and the
validation set are the same or similar. For diffusion problems like
chloride ingress, the diffusion coefficient is the most sensitive parameter
[103,106], i.e., its fitted value is highly dependent on the uncertainty of
the overall model. It is worth noting that the reliability of the model
decreases as its complexity increases, i.e., with the number of input
parameters required.
The fitting of total chloride profiles using mechanistic models to
obtain a diffusion coefficient is therefore misleading due to the un­
certainties in the chemical model. Instead, it is suggested that the
diffusion coefficient should be determined independently through other
methods. The use of electro-migration methods, as suggested in Section
2.3.2, by other researchers [64,107–109], and in the fib model code
[110,111], is of particular interest due to the relatively short time
required (~2 weeks) compared to natural diffusion (~3 months - 3
years).
3.1.2. Can chloride profiles be used to fit engineering properties?
Unlike mechanistic models, engineering models have only a single
equation with a single variable. This means that fitting these models to
chloride profiles can, in theory, provide two reliable parameters: the
amplitude (the amount of chloride) and the rate of the ingress (or,
equivalently, the penetration depth).
Due to the overall conservation of the typical diffusion profile shape,
Fick's second law is often used to model chloride profiles with the total
chloride content, C, as the main variable [97,110,112]:
∂C ∂2 C
= Dapp 2 (1)
∂t ∂x
where Dapp is an apparent diffusion coefficient, t is time, and x is the
ingress depth. In constant boundary conditions and with a semi-infinite
material, the following analytical solution exists, using the comple­
mentary error function (erfc):
( )
x
C(xt) = CS erfc √̅̅̅̅̅̅̅̅̅̅̅ (2)
2 Dapp t
where C(x,t) is the total chloride content at a depth x and time t, and the
fitting parameters are the apparent diffusion coefficient (Dapp) and the
surface concentration (Cs). Why are we able to fit two parameters in one
profile? This is because both the height and the depth of the profile can
be fitted, whereas in mechanistic models, the amplitude is fixed by the
chemical model and the porosity, which are assumed to be fixed prop­
erties of the material. However, it is important to assess the physical
meaning of all fitting parameters.
The surface concentration, Cs, has been used as an indication for the
total binding capacity [11]. However, our discussion on the impact of
exposure and more specifically leaching (Section 2.2.2) demonstrates
the limitations of this approach. In realistic conditions, the surface
concentration of chloride profiles does not reach a maximum at the
surface but slightly deeper. This is referred to as the “peaking behav­
iour”, see Section 2.2.2.3. The first few points of the profile near the
exposed surface typically need to be ignored to obtain a good fit with the
erfc function shape, as illustrated on Fig. 15. This means that Cs is only a
fitting parameter with no direct physical meaning.
The apparent diffusion coefficient is the parameter responsible for
the profile shape [61,97]. A lower apparent diffusion coefficient leads to
a sharper diffusion front, penetrating less into the sample. Although it
has the same unit [m2/s] and the same order of magnitude (~1.10− 12
m2/s), the apparent diffusion coefficient should not be confused with the
effective diffusion coefficient. The latter is used in mechanistic models
and, in theory, it represents only the effect of the pore network geometry
K. De Weerdt et al.
Fig. 15. Chloride profile fitted with the erfc function to obtain parameters
(Dapp, Cs, and xc).
and the particle-surface interactions. In contrast, the apparent diffusion
coefficient is a lumped parameter, representing both the transport co­
efficient and the effect of the binding, so its value depends on the
boundary conditions (composition of the exposure solution, tempera­
ture, and so on). However, it can be demonstrated that if the binding
isotherm is linear, the effective and apparent diffusion coefficients can
be related analytically [61,97]. Such a linear binding isotherm can be
obtained by assuming pH-dependent isotherms, as illustrated in Fig. 9.
Even though the apparent diffusion coefficient cannot be directly
related to intrinsic physical parameters, provided the measurements are
carried out in the same controlled conditions, the apparent diffusion
coefficient of samples can be compared to provide a classification of
cementitious systems [113]. For example, this allowed us to successfully
compare the impact of SCMs on the apparent diffusion coefficient (see
Section 2.3).
The final parameter in Fig. 15 is the penetration depth (xc). This
depth is found by assuming a reference chloride content and deter­
mining the corresponding ingress depth on the chloride profile through
interpolation. This reference chloride content is just a chosen total
chloride content and is therefore neither directly nor uniquely related to
the critical chloride threshold [61,114].
If chloride profiles are obtained after various exposure times, the
penetration depth can be collected, and then plotted as a function of the
( √̅̅)
square root of the exposure time (xc = f t ). As illustrated in Fig. 16b,
the points then align linearly as a function of the square root of time
[61,67,114–117]:
Fig. 16. The square root analysis, a) Master curve of chloride profiles for one system plotted as a function of x/ t , b) “Critical concentration” plotted as a function of
√̅̅
x vs. t and corresponding trend lines, with and without offset.
14
Cement and Concrete Research 173 (2023) 107287
( √̅ ) √̅
xc t =a t+b (3)
where xc is the penetration depth for a defined reference chloride con­
tent, t is time, a is a diffusivity coefficient, and b is the offset. The
diffusivity coefficient, a, is similar to the “carbonation” coefficient used
to compare cementitious systems and carbonation conditions [118,119],
though for carbonation, no offset b is considered.
A similar approach is to collapse the profiles collected at different
times for the same system and chloride exposure on to a “master curve”
√̅̅
by plotting along the x/ t axis (see Fig. 16a). This curve makes it
possible to fit a single Dapp (and Cs) for all the profiles independent of the
time of collection. Mathematically, this means we can still use Eq. (2),
√̅̅
but the variable is x/ t instead of x and t.
These approaches provide a good method for increasing the reli­
ability of the “diffusivity parameter” that describes the chloride profile,
because it uses data from several profiles. These master curves are an
excellent tool for assisting decision-making for the repair of structures or
estimating their remaining service life, e.g., by detecting significant
deviation in the expected behaviour, which could be attributed for
example to the occurrence of cracks.
Of course, the practical difficulty is to obtain several of these profiles
for the same system, which in this context refers to both the concrete
composition and the exposure, or in other words both the material pa­
rameters and the boundary conditions. Chloride content determination
is a laborious process. However, the square root approach based on xc
(the penetration depth for a defined reference chloride content) can also
be applied to (semi-)quantitative methods, such as silver nitrate spray­
ing [120], EPMA [121] or μXRF [122], which can be much less labour-
intensive than ordinary chloride profiles. There is also a lot of interest in
developing in-situ methods to measure chloride ingress, such as re­
sistivity [123–125] and chloride sensors [126,127].
The main uncertainty for these approaches is the time needed to
observe a meaningful evolution of the chloride ingress. For the square
root approach, this translates into the decision on whether to use an
offset b or not (see Fig. 16b). The offset can be attributed to an initial
period of fast ingress, a fitting artefact, or the effect of leaching (Section
2.2.2). Further research is needed to better understand the physical
meaning of these parameters.
3.2. Profiles as output: monitoring and predictions
3.2.1. Engineering models
Without prior knowledge, the application of engineering models
generally results in highly uncertain predictions. Since they rely on
√̅̅
K. De Weerdt et al.
fitting apparent parameters, they are highly dependent on the condi­
tions for which the calibration data were obtained. The range of material
(SCMs, w/c, curing, etc.) and boundary conditions (temperature, rela­
tive humidity, alkalinity, composition exposure solution, etc.) cannot be
fully represented. This is especially true when considering the ever-
widening range of new SCMs or the unfortunate consequences of
climate change on for example temperature and sea water composition.
However, it is reasonable to utilize a two-step process: calibration
and modelling. The calibration step uses at best data from the structures
at an early age and/or in-situ testing blocks from the same batch, though
often one has to rely on existing data of a similar concrete and exposure.
These constrained parameters are then used in the second step to model
the long-term behaviour of the concrete in these conditions. These
predictions (i.e., baseline behaviour) can then be compared to real
measurements to analyse the actual state of the concrete. The moni­
toring is of course easier with non-destructive methods [126]. In this
case, the parameters in the model can also be continuously updated
using further monitoring.
It has been observed that the apparent diffusion coefficient approach
does not work when using early-age experimental data to predict long-
term data. Indeed, the apparent diffusion coefficients typically decrease
significantly as a function of time at early ages [128–130], even when
the concrete is not subject to mechanical loading and thereby potential
crack formation, and kept in a controlled environment. This time-
dependent behaviour is usually attributed to the continuation of hy­
dration and the corresponding microstructural changes. In engineering
models, such as those used in the DuraCrete guidelines [131], which
provided the basis for the fib Model Code [110,111] and resulted in the
ISO standard [112], this is commonly taken into account by introducing
an aging coefficient, m:
(t )m
(4)
0
Dapp (t) = Dapp,0
t chloride diffusion. In this case, ̃
where Dapp,0 is a reference apparent diffusion coefficient at t0 , and m is
the aging coefficient, which is a fitting parameter.
It is clear that such aging coefficients are non-physical because this
mathematical expression is not bounded (i.e., D goes to 0). As such this
empirical approach is limited and prone to over-fitting. It only works
because these parameters are fitted to limited data. In particular, it has
been shown that long-term chloride profiles collapse to a master curve in
the square root view [61], which indicates a unique apparent diffusion
coefficient at late age (5 to 20+ years). Similarly, the Life 365 model
(www.life-365.org) uses an aging coefficient for up to 25 years, after
which the diffusion coefficient is considered constant. Nevertheless, the
early-age measurements (typically at <1 year) still show significant
differences from later ages (5, 10 and 20 years) for some systems [61].
The effects that lead to these differences in early-age investigations need
to be identified and quantified because they are especially important
with slow reacting SCMs such as fly ash, for SCM assessment, and for
formulation optimization.
3.2.2. Mechanistic models
To discuss mechanistic models in depth would require a review on its
own, so the aim of this section is more limited. Here we just want to
Fig. 17. The building blocks of a reactive transport model for chloride binding.
15
Cement and Concrete Research 173 (2023) 107287
describe how the experimental findings described in Section 2 can
provide input to improve the mechanistic models and to discuss the
further experiments required to this end. To structure this discussion, we
need to describe the building blocks of a reactive transport model. This is
illustrated in Fig. 17.
This model describes the flux of matter (ions, water, gas, etc.) that
contribute to two mechanisms: the transport (i.e., the movement of
mobile species), and the reactions (i.e., the phase changes, such as
precipitation or evaporation). The former is parameterized by the
transport properties (e.g., the diffusion coefficient), while the latter are
parameterized by the equilibrium conditions and the reaction path (i.e.,
the local equilibrium and kinetics). To better understand how such pa­
rameters are chosen for various physical problems, we recommend
reading publications that use a similar formalism for leaching, carbon­
ation, and chloride ingress [61,132,133]. To simplify our discussion
here, we note the diffusion coefficient D, and the binding term B.
We assume that each effect contributes to the overall parameter. For
example, we could write:
D = D0 ̃
daggregates ̃
dITZ ̃
dpaste geometry
̃
dsolution ̃
dcharged_surfaces + Dcracks (5)
In most models, the multiplication factors (̃ d) are lumped together in
a single complex parameter, like the pore connectivity presented in
Section 2.3.2, the formation factor [82], or one of the many definitions
of tortuosity [134]. However, to correctly take the wide variety of
binders into account, each term needs to be understood and modelled
separately.
A question to answer is how the exposure solution should be
modelled. Most “fully” mechanistic models use the Nernst-Planck
equation [135,136]. This equation couples the diffusion of multiple
ions to ensure the conservation of the electroneutrality of the pore so­
lution and the solids. Another simpler method is to consider only the
dsolution needs to consider the effect of the
other ions. In particular, it means that D is a function of the chloride
concentration (and the exposure solution), and therefore equivalent to
an apparent diffusion coefficient [135]. The importance of the coupling
between the diffusivity of multiple ions is related to our discussion in
Section 2 on the importance of pH and leaching. However, for modelling
purposes, the first order of magnitude is obtained by quantifying the
diffusion of chloride “on its own”, especially when comparing different
binders. The diffusion of the chloride ion is therefore the focus of this
section.
The second research question – What is the path for chloride transport?
- concerns the definition of the geometrical contribution of the pore
structure to the diffusion coefficient, D.
We first discuss normalization with respect to the binder content. In
modelling terms, this translates into how the aggregates should be
modelled. Aggregates are considered to be impermeable and not reac­
tive with regard to chlorides. This means that ̃
daggregates is a multiplication
factor that describes the reduction of the connected pore space, as well
as the increase in geometric tortuosity. For simple geometry, this can be
relatively easily resolved using a homogenization scheme [137]. Ho­
mogenization is a mathematical method for modelling the microstruc­
ture to predict the effective transport properties. However, concrete is a
K. De Weerdt et al.
very heterogeneous and multiscale material, so quantifying this effect is
much more difficult [138–141].
Aggregates can also have an effect on the diffusion in the binder due
to the presence of the ITZ. Depending on the conditions, the ITZ has been
described as either more or less permeable than the bulk paste [41,142].
There is still no consensus on the impact of the ITZ on the overall ingress,
especially since it is difficult to quantify. However, it has been shown
that the cement type has a stronger impact on chloride diffusion than the
ITZ [143]. Cracks and microcracks in the surface of the concrete might
also impact the chloride penetration depth, especially at an early age
[144,145].
Another important matter is where can chlorides diffuse in bulk cement
paste? This requires an understanding of the various pore classes as
determined from proton NMR relaxometry (1H NMR) measurements
[146], see Fig. 18. Capillary pores are the pores between the grains that
are left after the initial packing and the initial water-to-cement ratio.
Interhydrate pores are a subcategory of capillary pores and usually
defined as the pores between the agglomerates of hydration phases (such
as the C-A-S-H needles). Gel pores are the intrinsic porosity of the C-A-S-
H and are often described as the result of the poor crystallinity and poor
stacking of the C-A-S-H sheets. The final class is not a pore, but the
interlayer space in the C-A-S-H structure, where the water and ions are
only mobile through bond breaking. 1H NMR measurements are more
accurate than the more commonly used mercury intrusion porosimetry
(MIP) method, which can reliably capture only interhydrate and capil­
lary porosity due to the physical limitations of the pressure it uses [147].
MIP is therefore not a suitable method for analysing the effect of the pore
structure on the diffusion coefficient.
What is the impact of the various pores on chloride ingress? These pore
classes can be used in models to derive the effective transport properties
[139,148]. Since these pores have different geometries and different
sizes, their intrinsic diffusion coefficients are different by orders of
magnitude. Typically, the intrinsic diffusion coefficient of C-A-S-H gel
pores is around 10− 11–10− 12 m2/s, a similar order of magnitude to the
cement paste effective diffusion coefficient [141]. The diffusion coeffi­
cient for the capillary pores is assumed to be one to three orders of
magnitude higher depending on their characteristic pore size. Since the
Fig. 18. Pore classes in cement pastes revealed by Proton NMR Relaxometry and Mercury Intrusion Porosimetry.
16
Cement and Concrete Research 173 (2023) 107287
effective diffusion coefficient of cement pastes is close to the diffusivity
in C-A-S-H pores in most relevant systems, most models assume that
liquid diffusion is limited by the gel pores. This agrees with permeability
measurements [39].
Therefore, we need to estimate the volume fraction of capillary and
gel pores present, to obtain a first estimate of the effective diffusion
coefficient of a cement paste. This is challenging because it is difficult to
quantify the hydrate phase assemblage, especially the C-A-S-H due to its
variable composition and microcrystalline nature. Moreover, there are
two populations of C-A-S-H: the high-density C-A-S-H in the inner
product, and the low-density C-A-S-H in the outer product. It is unclear
how the inner and outer products contribute to the chloride transport.
Do they have different intrinsic diffusion coefficients? The development
of models combined with advances in quantification using advanced
characterization techniques might answer this question in the future.
This is especially important when considering blended cement sys­
tems, where SCMs lead to changes in the system by reducing the clinker
factor and changing the C-A-S-H quantity, composition, and pore
structure. Whether the space is filled with C-A-S-H, capillary pores, or
impermeable phases (e.g., AFm or unreacted SCM) will govern the
impact of SCMs on the geometric term of the effective diffusion coeffi­
cient. Advances in knowledge in the domain of hydration, microstruc­
ture and thermodynamic predictions [149] are therefore highly relevant
to obtaining quantitative models for the diffusion coefficients.
For the first research question - What is the contribution of chloride
binding to chloride transport? - we need to distinguish two contributions
to the chloride profiles: the mobile and the immobile chlorides, i.e. the
chloride that can contribute to transport, or not, in agreement with the
definition established in Fig. 17 Binding is commonly associated first
with immobile species, but this section highlights that there are two
types of binding: strong binding (immobile species), and weak binding
(mobile species).
Chemical binding is assumed to be strong binding, because the
chlorides are trapped in the interlayer of the AFm crystalline structure.
Physical binding in the C-A-S-H can be assumed to be weak binding,
because the most common model for physical binding assumes the
chlorides accumulate in the electrical double layer (EDL), i.e., in the
K. De Weerdt et al.
solution. However, a portion (~10–20 %) of the binding in C-A-S-H has
been shown to be irreversible, i.e., not taken into account in the water-
soluble test (see Fig. 11) [61]. This could indicate that, even though the
majority of physical binding should be modelled as weak binding, a
portion of the bound chloride in the C-A-S-H should be considered as
strong binding.
Strong binding makes two complementary contributions to the
chloride transport. First, it acts as a “storage” term (e.g., a sink initially,
a source during leaching). This contribution reduces the total flux of
chloride by reducing the amount of free chloride able to move further.
Second, at equilibrium it determines the concentration in the pore so­
lution and is therefore the driving factor for diffusion. To analyse the
effect of the strong binding, it is important to determine the equilibrium
between the pore solution and the solid phases. This is particularly
challenging due to the presence of solid solutions, i.e., FSss (see Sections
2.2 and 2.3). From the modelling point of view, this means that to
predict diffusion, we need accurate chemical models to determine the
FSss in equilibrium with the solution so that we can predict the strong
binding.
The contribution of the weak binding to chloride ingress is the change
in the mobility of ions. Due to the presence of charged surfaces, ions are
going to be attracted to or repulsed from the EDL [78,79]. This effect is
only dominant when the pore size is sufficiently small compared to the
EDL size (~1 nm) [52,53]. To properly determine the effect of the
physically bound chloride on chloride ingress, we need to model the
impact of the charged surface on the diffusion coefficient. More specif­
ically, there are two challenges. Firstly, we need to determine the
amount of surface and its state (i.e., the density of charges); and sec­
ondly, the reduction of mobility of ions in the presence of this surface.
This charged-surface effect needs to be included (̃ dcharged_surfaces ) to enable
the model to predict the impact of changes in the C-A-S-H composition
and densities (i.e., packing) on chloride transport. The C-A-S-H
composition and densities strongly depend on both the presence of any
SCMs (due to their wide range of composition and pozzolanic activity)
and the exposure conditions (i.e., any leaching of hydroxyl ions).
And finally, how does this feed into to our third research question -
How are our findings on chloride profiles also important for corrosion?
For engineering models, we need expressions we can easily relate to
total chloride content per binder or concrete. In that respect, the total
chloride content/binder content [95] and the total chloride content/
neutralization potential [96] are promising. Both can easily be linked to
measured chloride profiles and are relatively easy to determine experi­
mentally. The latter also considers variations in the passivation capacity
of different binders.
For mechanistic models, which in theory can predict the pore solu­
tion composition in exposed concrete through advanced chemical
models that take into account binding and interactions with the envi­
ronment such as leaching, the expression [Cl− ]/[OH− ] may be
preferred. This expression also directly links to corrosion science models
and experiments [150].
Considering that the chloride concentration is only one of many
factors affecting reinforcement corrosion initiation [45,46], future
mechanistic models should ideally also be able to predict other equally
important factors such as the moisture conditions, availability of oxygen
and concrete resistivity in the vicinity of the reinforcement, which are
required to be able to calculate a probability of corrosion initiation.
3.3. Implications for engineering practice
3.3.1. Which part of the chloride profile is relevant for engineering models?
Traditionally, the surface (binding capacity) and the tail end (ingress
depth) of a chloride profile are used for engineering models. In fact,
however, neither should be used. The profile near the exposed surface is
likely to be affected by an increased cement content in the concrete due
to the “wall effect”. The tail-end of the profiles (low chloride content) is
17
Cement and Concrete Research 173 (2023) 107287
subject to heterogeneity effects and the imprecision of the experimental
protocols. It is possible to normalize to the binder content, but this is not
straightforward due, for example, to leaching. Chloride profiles also
tend to exhibit “peaking behaviour” near the exposed surface, which
means that the total chloride content is lower at the surface than in the
following sections deeper in. We attribute this peaking behaviour to
leaching because severe leaching at the surface (pH < 10.5) leads a loss
of the chloride-binding capacity of the paste, whereas moderate leaching
(pH > 12.4) slightly deeper in can lead to enhanced binding. Given the
variation in paste content and the effect of leaching, it is clear that the
total chloride content near the surface is governed by binding and that it
does not represent a “driving potential” for chloride ingress.
In contrast, we argued that the central part of the profile is the most
indicative of the material's chloride resistance in a given environment. In
√̅̅
the square root approach to modelling, the profiles overlap on the x/ t
view, indicating that a single lump parameter can be used to quantita­
√̅̅
tively describe the profiles. The x/ t master curve also enables to
identify which points at the surface or at the tail of the curve should be
considered in the fitting process as several profiles can be directly
√̅̅
compared. The x/ t master curve is also the best option for defining
what the surface and tail parts of the curve mean. The lump parameter is
either the apparent diffusion coefficient (the erfc solution of 2nd Fick's
√̅̅
law) or the diffusivity coefficient (the slope in the xc vs. t approach).
These lump parameters depend on the exposure conditions, so they are
not intrinsic material properties, but they can be used to classify
cementitious systems when measurements are carried out in the same
conditions. The square root approach is more reliable, but more time-
consuming because it requires several profiles.
These engineering models can also be used for predicting chloride
profiles, though they do require sufficient “early-age” data on similar
concrete in the same exposure to reliably calibrate the models. When
applied correctly, they can be a very valuable engineering tool for the
maintenance and repair planning of existing structures. We want to
underline that calibration data for the same exposure is needed, which is
a true challenge when making detailed engineering predictions of
chloride ingress for a real structure due to the high variability in the
exposure conditions both on the structure (e.g. surface orientation and
height) and in time.
3.3.2. Knowledge gaps
Sufficient “early-age” data is the core of the issue because current
engineering approaches rely on an aging coefficient, or an offset in the
square root approach. The main issue is that these empirical coefficients
require the measurement of several profiles to reliably identify these
parameters. The challenge is due to both the complexity and the
destructive aspects of the current methods of obtaining these profiles.
The solution is either to identify the causes of these early-age effects and
propose a flexible model, or to develop fast non-destructive methods for
measuring the profiles.
4. Summary and perspectives
This paper presents how a series of case studies brought us to a better
understanding of chloride profiles in concrete, as schematically illus­
trated in Fig. 19. We also reflect on the use of chloride profiles in en­
gineering and mechanistic models and highlight the crucial knowledge
gaps encountered. The paper evolves around three central questions, the
answers to which are summarized below.
4.1. What is the contribution of chloride binding to chloride transport?
We are able to determine chloride profiles thanks to the interactions
between chlorides and cement hydrates, i.e., chemical binding (in Cl-
AFm) and physical binding (on C-A-S-H) (see Fig. 19) because only a
small fraction of the chlorides are found in the capillary pores (in the
K. De Weerdt et al.
Fig. 19. Concluding sketch of a chloride profile from a concrete element sub­
merged in sea water at Solsvik field station for 16 years [2], which illustrates
our gained understanding compared to Fig. 1.
pore solution).
The exposure case studies showed that the total chloride content near
the surface is strongly affected by variations in the amount of bound
chloride due to, on the one hand, the “wall effect”, which causes a higher
paste content near the surface, and on the other hand, leaching, which
causes increased binding with moderate leaching (pH > 12.4) or
reduced binding with severe leaching (pH < 10.5). These variations
result in the “peaking effect” typically observed near the exposed
surface.
This means that the total chloride content near the surface does not
represent a “driving potential” for chloride ingress. This was confirmed
in the binder case study, where the chloride profiles of cement pastes
with various SCMs exposed to 0.5 M NaCl all showed very similar total
chloride contents at the surface and similar binding capacities under
equilibrium conditions, even though the ingress depths varied greatly.
Nevertheless, chloride binding does affect chloride ingress. This ef­
fect is best understood by looking at the distribution of chlorides be­
tween the pore solution, the Cl-AFm, and the C-A-S-H. The binder case
study showed that the distribution can vary significantly between
binders. The binder impacts the amounts of Cl-AFm and C-A-S-H. For
example, the white Portland cement seems to form significantly more C-
A-S-H than the blended systems. Moreover, the binder and the pH affect
the amount of chloride taken up per unit mass of Cl-AFm and of C-A-S-H.
For mechanistic models, the total chlorides need to be divided into
strongly bound and weakly bound chlorides (see Fig. 19). The binder
case study showed that the strongly bound chlorides, i.e., chlorides in
the AFm interlayer and 10–20 % of chlorides in the C-A-S-H, can be
considered immobile. In a mechanistic transport model, they would end
up in a storage term. The weakly bound chlorides (i.e., most chlorides
adsorbed on the C-A-S-H) will contribute to the transport, but at a slower
rate than the free chlorides.
4.2. What is the path for chloride transport?
By investigating various blended cement pastes and w/b ratios, we
showed that the chloride penetration depth after exposure a 0.5 M NaCl
solution was strongly correlated with the bulk electrical conductivity.
Since this value (in the absence of chlorides) combines the influence of
both the pore network and the pore solution, we can conclude that these
18
Cement and Concrete Research 173 (2023) 107287
two parameters comprise the chloride ingress resistance of paste. In
other words, the chloride penetration resistance can be assessed without
knowledge of binding properties. Such knowledge is crucial to under­
standing the path for chloride transport.
The exposure case studies showed that the ingress of chloride anions
is not followed equimolarly by cations such as sodium. Instead, we found
it was linked to hydroxyl leaching. We demonstrated that limiting
leaching reduced the ingress and binding of chlorides in concrete,
whereas increased leaching promoted them. This also shows how
important pore solution conductivity is for assessing chloride ingress.
When we compared concretes exposed to sea water and NaCl solu­
tion, we observed that with sea water exposure the precipitation of
phases near the concrete surface partially filled larger voids and cracks,
but that this did not limit the chloride ingress compared to NaCl expo­
sure for which no precipitation was observed. This indicates that chlo­
ride ingress is not affected by a reduction in the coarser porosity, but is
governed by transport in the finer pores, i.e., those associated with the C-
A-S-H phase. Similarly, the higher chloride ingress observed in Portland
cement pastes than in blended cements might be associated with their
higher C-A-S-H content.
Mechanistic models describe the transport of chloride ions using the
intrinsic diffusion coefficient, which is linked to the pore structure of the
cement paste. Porosity can be divided into a number of pore classes
according to their morphology. Diffusivity depends on the mobility in all
the different types of pores. Although the mobility of chloride in the gel
pores associated with C-A-S-H is less than in larger pores, the contri­
bution of the gel pores to chloride transport seems to be crucial because
they represent such a large part of the porosity in hydrated cement paste.
4.3. How are our findings on chloride profiles relevant for corrosion of the
reinforcement?
The understanding of chloride profiles described in this paper can
help us select a meaningful expression for Ccrit for use in estimating the
risk of corrosion from chloride profiles. First, when we compare Ccrit for
different concretes, we should normalize it to the cement paste content
or even to the content of hydration products if a considerable part of the
cement has not reacted (e.g., blended cement with high SCM content).
Second, to express Ccrit we need a better understanding of the distribu­
tion of chlorides and their role in corrosion initiation. This issue is
strongly related to the understanding of chloride binding, i.e., how the
pore solution interacts with the solid phases and the influence of
changes in pH (e.g., leaching). Third, the hydroxyl concentration of the
pore solution and the acid neutralization capacity of the binder are both
measures for the corrosion inhibition potential of the binder. Taking this
into account, a definition of Ccrit as a ratio of the chloride content vs. the
inhibition potential seems more appropriate. Combining all these ob­
servations, the expression of Ccrit as the total chloride content normal­
ized to the acid neutralization potential might be preferred because it is
independent of the binder content, it considers a corrosion inhibition
potential, it is relatively easy to determine, and it can be linked to a
chloride profile because it uses similar units.
Mechanistic models can open up for a much larger range of expres­
sions for Ccrit because they can take into account complex chloride-
binding behaviour, leaching, and can predict pore solution composi­
tions in the vicinity of the reinforcement.
4.4. What next?
We have seen that strongly bound chlorides (Cl-AFm) and “mobile”
chlorides (in the C-A-S-H and in the pore solution) play different roles in
transport and potentially in corrosion. This should be taken into account
in upcoming mechanistic models. However, experimental validation of
these models will require the use of advanced experimental methods,
some of which exist but are still challenging to use.
This is particularly important in blended cement systems because
K. De Weerdt et al.
SCMs affect several parameters related to reactive transport, such as: (1)
the amount and the stoichiometry of the Cl-AFm; (2) the amount of C-A-
S-H formed and its composition and spatial distribution; (3) the pore
solution in equilibrium with the solids; and (4) the pore structure and
therefore its diffusivity and transport properties.
This paper has demonstrated the crucial role of C-A-S-H in chloride
transport in concrete. It is vital that we obtain a better understanding of
the impact of differences in C-A-S-H composition and structure on
chloride transport properties by using advanced experiments and
models. Including this understanding in self-sufficient reactive transport
approaches by combining the elements discussed above concerning the
inherent heterogeneity of concrete is the next big challenge we face.
CRediT authorship contribution statement
Klaartje De Weerdt: Conceptualization, Writing – original draft,
Writing – review & editing, Visualization. William Wilson: Conceptu­
alization, Writing – original draft, Writing – review & editing, Visuali­
zation. Alisa Machner: Conceptualization, Writing – original draft,
Writing – review & editing, Visualization. Fabien Georget: Conceptu­
alization, Writing – original draft, Writing – review & editing,
Visualization.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cemconres.2023.107287.
References
[1] U.M. Angst, Challenges and opportunities in corrosion of steel in concrete, Mater.
Struct. 51 (2018) 4, https://doi.org/10.1617/s11527-017-1131-6.
[2] K. De Weerdt, D. Orsáková, A.C.A. Müller, C.K. Larsen, B.M. Pedersen, M.
R. Geiker, Towards the understanding of chloride profiles in marine exposed
concrete, impact of leaching and moisture content, Constr. Build. Mater. 120
(2016) 418–431, https://doi.org/10.1016/j.conbuildmat.2016.05.069.
[3] NORDTEST, NT BUILD 443 Concrete, Hardened: Accelerated Chloride
Penetration, Concrete, Hardened, NORDTEST, Finland, 1995.
[4] ASTM, C1556-11a, Standard Test Method for Determining the Apparent Chloride
Diffusion Coefficient of Cementitious Mixtures by Bulk Diffusion, ASTM
International, 2016.
[5] EN 12390-11: Testing hardened concrete - Part 11: Determination of the chloride
resistance of concrete, unidirectional diffusion, CEN/TC 104, 2015.
[6] C. Shi, Q. Yuan, F. He, X. Hu, Transport and Interactions of Chlorides in Cement-
Based Materials, CRC Press, London, 2021.
[7] L. Tang, L.-O. Nilsson, P.A. Muhammed Basheer, Resistance of Concrete to
Chloride Ingress – Testing and Modelling, CRC Press, London, 2017.
[8] L. Bertolini, B. Elsener, P. Pedeferri, E. Redaelli, R.B. Polder, Corrosion of Steel in
Concrete: Prevention, Diagnosis, Repair, 2nd edition, WILEY-VCH, Singapore,
2014.
[9] H. Justnes, A review of chloride binding in cementitious systems, Nord. Concr.
Res. 21 (1998) 48–63.
[10] Q. Yuan, C. Shi, G. De Schutter, K. Audenaert, D. Deng, Chloride binding of
cement-based materials subjected to external chloride environment – a review,
Constr. Build. Mater. 23 (2009) 1–13, https://doi.org/10.1016/j.
conbuildmat.2008.02.004.
[11] H. Zibara, Binding of External Chlorides by Cement Pastes, PhD thesis
Department of Civil Engineering,, University of Toronto, Canada, 2001.
[12] M. Balonis, B. Lothenbach, G. Le Saout, F.P. Glasser, Impact of chloride on the
mineralogy of hydrated Portland cement systems, Cem. Concr. Res. 40 (2010)
1009–1022, https://doi.org/10.1016/j.cemconres.2010.03.002.
[13] U.A. Birnin-Yauri, F.P. Glasser, Friedel’s salt, Ca2Al(OH)6(Cl,OH)⋅2H2O: its solid
solutions and their role in chloride binding, Cem. Concr. Res. 28 (1998)
1713–1723, https://doi.org/10.1016/S0008-8846(98)00162-8.
19
Cement and Concrete Research 173 (2023) 107287
[14] F.P. Glasser, A. Kindness, S.A. Stronach, Stability and solubility relationships in
AFm phases: part I. Chloride, sulfate and hydroxide, Cement Concr. Res. 29
(1999) 861–866, https://doi.org/10.1016/S0008-8846(99)00055-1.
[15] M.Y. Hobbs, Solubilities and Ion Exchange Properties of Solid Solutions Between
the Hydroxyl, Chlorine and Carbontrioxide End Members of the Monocalcium
Aluminate Hydrates, PhD thesis, University of Waterloo, Canada, 2001.
[16] H. Pöllmann, Mischkristallbildung in den Systemen 3CaO⋅Al2O3⋅CaCl2⋅10H2O –
3CaO⋅Al2O3⋅CaCO3⋅11H2O und 3CaO⋅Al2O3⋅CaCl2⋅10H2O – 3CaO⋅Al2O3⋅Ca
(OH)2⋅12H2O, PhD thesis, University of Erlangen-Nuremberg, Germany, 1980.
[17] H. Pöllmann, Solid solutions of complex calcium aluminate hydrates containing
Cl− , OH− and CO2− 3 anions, in: 8th International Congress on the Chemistry of
Cement Rio de Janeiro, 1986, pp. 300–306.
[18] C. Arya, N.R. Buenfeld, J.B. Newman, Factors influencing chloride-binding in
concrete, Cem. Concr. Res. 20 (1990) 291–300, https://doi.org/10.1016/0008-
8846(90)90083-A.
[19] A. Delagrave, J. Marchand, J.-P. Ollivier, S. Julien, K. Hazrati, Chloride binding
capacity of various hydrated cement paste systems, Adv. Cem. Based Mater. 6
(1997) 28–35, https://doi.org/10.1016/S1065-7355(97)90003-1.
[20] O. Wowra, M.J. Setzer, Sorption of chlorides on hydrated cement and C3S pastes,
in: M.J. Setzer, R. Auberg (Eds.), Frost Resistance of Concrete, E & FN Spon,
London, 1997, pp. 147–153.
[21] K. De Weerdt, D. Orsáková, M.R. Geiker, The impact of sulphate and magnesium
on chloride binding in Portland cement paste, Cem. Concr. Res. 65 (2014) 30–40,
https://doi.org/10.1016/j.cemconres.2014.07.007.
[22] C. Labbez, A. Nonat, I. Pochard, B. Jönsson, Experimental and theoretical
evidence of overcharging of calcium silicate hydrate, J. Colloid Interface Sci. 309
(2007) 303–307, https://doi.org/10.1016/j.jcis.2007.02.048.
[23] G. Plusquellec, A. Nonat, Interactions between calcium silicate hydrate (C-S-H)
and calcium chloride, bromide and nitrate, Cem. Concr. Res. 90 (2016) 89–96,
https://doi.org/10.1016/j.cemconres.2016.08.002.
[24] S. Barzgar, B. Lothenbach, M. Tarik, A. Di Giacomo, C. Ludwig, The effect of
sodium hydroxide on Al uptake by calcium silicate hydrates (CSH), J. Colloid
Interface Sci. 572 (2020) 246–256, https://doi.org/10.1016/j.jcis.2020.03.057.
[25] J. Haas, A. Nonat, From C–S–H to C–A–S–H: Experimental study and
thermodynamic modelling, Cem. Concr. Res. 68 (2015) 124–138, https://doi.
org/10.1016/j.cemconres.2014.10.020.
[26] I. Galan, L. Perron, F.P. Glasser, Impact of chloride-rich environments on cement
paste mineralogy, Cem. Concr. Res. 68 (2015) 174–183, https://doi.org/
10.1016/j.cemconres.2014.10.017.
[27] C. Jones, S. Ramanathan, P. Suraneni, W.M. Hale, Calcium oxychloride: a critical
review of the literature surrounding the formation, deterioration, testing
procedures, and recommended mitigation techniques, Cem. Concr. Compos. 113
(2020), 103663, https://doi.org/10.1016/j.cemconcomp.2020.103663.
[28] Y. Elakneswaran, T. Nawa, K. Kurumisawa, Electrokinetic potential of hydrated
cement in relation to adsorption of chlorides, Cem. Concr. Res. 39 (2009)
340–344, https://doi.org/10.1016/j.cemconres.2009.01.006.
[29] K. De Weerdt, H. Justnes, M.R. Geiker, Changes in the phase assemblage of
concrete exposed to sea water, Cem. Concr. Compos. 47 (2014) 53–63, https://
doi.org/10.1016/j.cemconcomp.2013.09.015.
[30] U.H. Jakobsen, K. De Weerdt, M.R. Geiker, Elemental zonation in marine
concrete, Cem. Concr. Res. 85 (2016) 12–27, https://doi.org/10.1016/j.
cemconres.2016.02.006.
[31] C. Gallé, Effect of drying on cement-based materials pore structure as identified
by mercury intrusion porosimetry: a comparative study between oven-, vacuum-,
and freeze-drying, Cem. Concr. Res. 31 (2001) 1467–1477, https://doi.org/
10.1016/S0008-8846(01)00594-4.
[32] EN 1992-1-1:2004/A1 Design of concrete structures - Part 1-1: General rules and
rules for buildings, CEN, 2014.
[33] EN 206:2013+A2: Concrete Specification, performance, production and
conformity, CEN, 2021.
[34] CSA A23.1/CSA A23.2. Concrete materials and methods of concrete construction/
Test methods and standard practices for concrete, CSA Group, 2019.
[35] T.C. Powers, T.L. Brownyard, Studies of the physical properties of hardened
Portland cement paste, ACI J. Proceedings 43 (1946) 249–336, https://doi.org/
10.14359/15301.
[36] D.P. Bentz, E.F. Irassar, B.E. Bucher, W.J. Weiss, Limestone fillers conserve
cement; part 1: an analysis based on Powers’ model, Concr. Int. 31 (2009) 41–46.
[37] P. Halamickova, R.J. Detwiler, D.P. Bentz, E.J. Garboczi, Water permeability and
chloride ion diffusion in Portland cement mortars: relationship to sand content
and critical pore diameter, Cem. Concr. Res. 25 (1995) 790–802, https://doi.org/
10.1016/0008-8846(95)00069-O.
[38] R.A. Cook, K.C. Hover, Mercury porosimetry of hardened cement pastes, Cem.
Concr. Res. 29 (1999) 933–943, https://doi.org/10.1016/S0008-8846(99)00083-
6.
[39] W. Vichit-Vadakan, G.W. Scherer, Measuring permeability of rigid materials by a
beam-bending method: III, cement paste, J. Am. Ceram. Soc. 85 (2002)
1537–1544, https://doi.org/10.1111/j.1151-2916.2002.tb00309.x.
[40] L. Tang, Chloride Ingress in Concrete Exposed to Marine Environment - Field Data
up to 10 Years Exposure, SP Report, SP Swedish National Testing and Research
Institute, 2003, p. 68.
[41] K.L. Scrivener, A.K. Crumbie, P. Laugesen, The interfacial transition zone (ITZ)
between cement paste and aggregate in concrete, Interf. Sci. 12 (2004) 411–421,
https://doi.org/10.1023/B:INTS.0000042339.92990.4c.
[42] K. De Weerdt, M. Bernhardt, M.R. Geiker, O. Skjolsvold, K.O. Kjellsen, Influence
of cast and cut surface on chloride ingress resistance of concrete in marine splash
zone, in: 4th International Conference on Sustainable Construction Materials and
K. De Weerdt et al.
Technologies, Las Vegas, 2016, pp. 1561–1568, https://doi.org/10.18552/2016/
SCMT4D181.
[43] S. Fjendbo, K. De Weerdt, H.E. Sørensen, M.R. Geiker, When and how should
chloride profiles be calibrated for paste fraction? Nord. Concr. Res. 66 (2022)
1–18, https://doi.org/10.2478/ncr-2021-0021.
[44] U. Angst, B. Elsener, C.K. Larsen, Ø. Vennesland, Critical chloride content in
reinforced concrete — a review, Cem. Concr. Res. 39 (2009) 1122–1138, https://
doi.org/10.1016/j.cemconres.2009.08.006.
[45] U.M. Angst, M.R. Geiker, A. Michel, C. Gehlen, H. Wong, O.B. Isgor, B. Elsener, C.
M. Hansson, R. François, K. Hornbostel, R. Polder, M.C. Alonso, M. Sanchez, M.
J. Correia, M. Criado, A. Sagüés, N. Buenfeld, The steel–concrete interface, Mater.
Struct. 50 (2017) 143, https://doi.org/10.1617/s11527-017-1010-1.
[46] U.M. Angst, M.R. Geiker, M.C. Alonso, R. Polder, O.B. Isgor, B. Elsener, H. Wong,
A. Michel, K. Hornbostel, C. Gehlen, R. François, M. Sanchez, M. Criado,
H. Sørensen, C. Hansson, R. Pillai, S. Mundra, J. Gulikers, M. Raupach,
J. Pacheco, A. Sagüés, The effect of the steel–concrete interface on chloride-
induced corrosion initiation in concrete: a critical review by RILEM TC 262-SCI,
Mater. Struct. 52 (2019) 88, https://doi.org/10.1617/s11527-019-1387-0.
[47] K. De Weerdt, M.B. Haha, G. Le Saout, K.O. Kjellsen, H. Justnes, B. Lothenbach,
Hydration mechanisms of ternary Portland cements containing limestone powder
and fly ash, Cem. Concr. Res. 41 (2011) 279–291, https://doi.org/10.1016/j.
cemconres.2010.11.014.
[48] F.J. Millero, R. Feistel, D.G. Wright, T.J. McDougall, The composition of standard
seawater and the definition of the reference-composition salinity scale, Deep-Sea
Res. I Oceanogr. Res. Pap. 55 (2008) 50–72, https://doi.org/10.1016/j.
dsr.2007.10.001.
[49] K. De Weerdt, B. Lothenbach, M.R. Geiker, Comparing chloride ingress from
seawater and NaCl solution in Portland cement mortar, Cem. Concr. Res. 115
(2019) 80–89, https://doi.org/10.1016/j.cemconres.2018.09.014.
[50] A. Machner, M.H. Bjørndal, H. Justnes, L. Hanžič, A. Šajna, Y. Gu, B. Bary, M. Ben
Haha, M.R. Geiker, K. De Weerdt, Effect of leaching on the composition of
hydration phases during chloride exposure of mortar, Cem. Concr. Res. 153
(2022), 106691, https://doi.org/10.1016/j.cemconres.2021.106691.
[51] W.M. Haynes, Handbook of Chemistry and Physics, 94th ed, CRC Press/Taylor
and Francis, 2013.
[52] Y. Yang, R.A. Patel, S.V. Churakov, N.I. Prasianakis, G. Kosakowski, M. Wang,
Multiscale modeling of ion diffusion in cement paste: electrical double layer
effects, Cem. Concr. Compos. 96 (2019) 55–65, https://doi.org/10.1016/j.
cemconcomp.2018.11.008.
[53] K. Ferjaoui, Nanoscale Modelling of Ionic Transport in the Porous C-S-H Network,
PhD thesis, EPFL, Switzerland, 2022, https://doi.org/10.5075/epfl-thesis-9955.
[54] K. De Weerdt, E. Bernard, W. Kunther, M.T. Pedersen, B. Lothenbach, Phase
changes in cementitious materials exposed to saline solutions, Cem. Concr. Res.
165 (2023), 107071, https://doi.org/10.1016/j.cemconres.2022.107071.
[55] A. Machner, M. Bjørndal, A. Šajna, N. Mikanovic, K. De Weerdt, Impact of
leaching on chloride ingress profiles in concrete, Mater. Struct. 55 (2021) 8,
https://doi.org/10.1617/s11527-021-01730-w.
[56] P. Hemstad, A. Machner, K. De Weerdt, The effect of artificial leaching with HCl
on chloride binding in ordinary Portland cement paste, Cem. Concr. Res. 130
(2020), 105976, https://doi.org/10.1016/j.cemconres.2020.105976.
[57] A. Machner, P. Hemstad, K. De Weerdt, Towards the understanding of the pH
dependency of the chloride binding of Portland cement pastes, Nord. Concr. Res.
58 (2018) 143–162, https://doi.org/10.2478/ncr-2018-0009.
[58] F. Georget, C. Bénier, W. Wilson, K.L. Scrivener, Chloride sorption by C-S-H
quantified by SEM-EDX image analysis, Cem. Concr. Res. 152 (2022), 106656,
https://doi.org/10.1016/j.cemconres.2021.106656.
[59] Q. Zhu, L. Jiang, Y. Chen, J. Xu, L. Mo, Effect of chloride salt type on chloride
binding behavior of concrete, Constr. Build. Mater. 37 (2012) 512–517, https://
doi.org/10.1016/j.conbuildmat.2012.07.079.
[60] A. Machner, M. Zajac, M. Ben Haha, K.O. Kjellsen, M.R. Geiker, K. De Weerdt,
Chloride-binding capacity of hydrotalcite in cement pastes containing dolomite
and metakaolin, Cem. Concr. Res. 107 (2018) 163–181, https://doi.org/10.1016/
j.cemconres.2018.02.002.
[61] F. Georget, W. Wilson, T. Matschei, Long-Term Extrapolation of Chloride Ingress:
An Illustration of the Feasibility and Pitfalls of the Square Root Law, Cem. Concr.
Res. 170 (2023) 107187, https://doi.org/10.1016/j.cemconres.2023.107187.
[62] K. De Weerdt, Chloride binding in concrete: recent investigations and recognised
knowledge gaps: RILEM Robert L’Hermite Medal Paper 2021, Mater. Struct. 54
(2021) 214, https://doi.org/10.1617/s11527-021-01793-9.
[63] M.D.A. Thomas, J.D. Matthews, Performance of pfa concrete in a marine
environment––10-year results, Cem. Concr. Compos. 26 (2004) 5–20, https://doi.
org/10.1016/S0958-9465(02)00117-8.
[64] W. Wilson, F. Georget, K. Scrivener, Unravelling chloride transport/
microstructure relationships for blended-cement pastes with the mini-migration
method, Cem. Concr. Res. 140 (2021), 106264, https://doi.org/10.1016/j.
cemconres.2020.106264.
[65] W. Wilson, J.N. Gonthier, F. Georget, K.L. Scrivener, Insights on chemical and
physical chloride binding in blended cement pastes, Cem. Concr. Res. 156 (2022),
106747, https://doi.org/10.1016/j.cemconres.2022.106747.
[66] C1218/C1218M-20 ASTM. Standard Test Method for Water-Soluble Chloride in
Mortar and Concrete, ASTM International, 2020.
[67] W. Wilson, F. Georget, K.L. Scrivener, Xcr/√t as an indicator of the Resistance
against Bulk Chloride Diffusion, Synercrete’23 - Interdisciplinary Approaches for
Cement-Based Materials and Structural Concrete: Synergizing Expertise and
Bridging Scales of Space and Time, Greece, 2023.
[68] W. Wilson, F. Georget, K.L. Scrivener, Manuscript Under Preparation, 2023.
20
Cement and Concrete Research 173 (2023) 107287
[69] A. Mesbah, C. Cau-dit-Coumes, F. Frizon, F. Leroux, J. Ravaux, G. Renaudin,
A new investigation of the Cl− –CO32− substitution in AFm phases, J. Am. Ceram.
Soc. 94 (2011) 1901–1910, https://doi.org/10.1111/j.1551-2916.2010.04305.x.
[70] A. Babaahmadi, A. Machner, W. Kunther, J. Figueira, P. Hemstad, K. De Weerdt,
Chloride binding in Portland composite cements containing metakaolin and silica
fume, Cem. Concr. Res. 161 (2022), 106924, https://doi.org/10.1016/j.
cemconres.2022.106924.
[71] F. Georget, B. Lothenbach, W. Wilson, F. Zunino, K.L. Scrivener, Stability of
hemicarbonate under cement paste-like conditions, Cem. Concr. Res. 153 (2022),
106692, https://doi.org/10.1016/j.cemconres.2021.106692.
[72] S. Sui, W. Wilson, F. Georget, H. Maraghechi, H. Kazemi-Kamyab, W. Sun,
K. Scrivener, Quantification methods for chloride binding in Portland cement and
limestone systems, Cem. Concr. Res. 125 (2019), 105864, https://doi.org/
10.1016/j.cemconres.2019.105864.
[73] F. Georget, W. Wilson, K.L. Scrivener, Edxia: microstructure characterisation from
quantified SEM-EDS hypermaps, Cem. Concr. Res. 141 (2021), 106327, https://
doi.org/10.1016/j.cemconres.2020.106327.
[74] Z. Shi, M.R. Geiker, B. Lothenbach, K. De Weerdt, S.F. Garzón, K. Enemark-
Rasmussen, J. Skibsted, Friedel’s salt profiles from thermogravimetric analysis
and thermodynamic modelling of Portland cement-based mortars exposed to
sodium chloride solution, Cem. Concr. Compos. 78 (2017) 73–83, https://doi.
org/10.1016/j.cemconcomp.2017.01.002.
[75] J. Tritthart, Chloride binding in cement II. The influence of the hydroxide
concentration in the pore solution of hardened cement paste on chloride binding,
Cement Concr. Res. 19 (1989) 683–691, https://doi.org/10.1016/0008-8846(89)
90039-2.
[76] Z. Shi, M.R. Geiker, K. De Weerdt, T.A. Østnor, B. Lothenbach, F. Winnefeld,
J. Skibsted, Role of calcium on chloride binding in hydrated Portland
cement–metakaolin–limestone blends, Cem. Concr. Res. 95 (2017) 205–216,
https://doi.org/10.1016/j.cemconres.2017.02.003.
[77] J.J. Beaudoin, V.S. Ramachandran, R.F. Feldman, Interaction of chloride and
CSH, Cem. Concr. Res. 20 (1990) 875–883, https://doi.org/10.1016/0008-8846
(90)90049-4.
[78] Y. Elakneswaran, A. Iwasa, T. Nawa, T. Sato, K. Kurumisawa, Ion-cement hydrate
interactions govern multi-ionic transport model for cementitious materials, Cem.
Concr. Res. 40 (2010) 1756–1765, https://doi.org/10.1016/j.
cemconres.2010.08.019.
[79] S. Yoshida, Y. Elakneswaran, T. Nawa, Electrostatic properties of C–S–H and C-A-
S-H for predicting calcium and chloride adsorption, Cem. Concr. Compos. 121
(2021), 104109, https://doi.org/10.1016/j.cemconcomp.2021.104109.
[80] Y. Zhou, D. Hou, J. Jiang, L. Liu, W. She, J. Yu, Experimental and molecular
dynamics studies on the transport and adsorption of chloride ions in the nano-
pores of calcium silicate phase: the influence of calcium to silicate ratios,
Microporous Mesoporous Mater. 255 (2018) 23–35, https://doi.org/10.1016/j.
micromeso.2017.07.024.
[81] G.E. Archie, The electrical resistivity log as an aid in determining some reservoir
characteristics, Trans. AIME 146 (1942) 54–62, https://doi.org/10.2118/
942054-g.
[82] R. Spragg, C. Qiao, T. Barrett, J. Weiss, 11 - Assessing a concrete's resistance to
chloride ion ingress using the formation factor, in: A. Poursaee (Ed.), Corrosion of
Steel in Concrete Structures, Woodhead Publishing, Oxford, 2016, pp. 211–238.
[83] E.J. Garboczi, Permeability, diffusivity, and microstructural parameters: a critical
review, Cem. Concr. Res. 20 (1990) 591–601, https://doi.org/10.1016/0008-
8846(90)90101-3.
[84] W.J. Weiss, R.P. Spragg, O.B. Isgor, M.T. Ley, T. Van Dam, Toward performance
specifications for concrete: linking resistivity, RCPT and diffusion predictions
using the formation factor for use in specifications, in: D.A. Hordijk, M. Luković
(Eds.), High Tech Concrete: Where Technology and Engineering Meet,
Proceedings of the 2017 Fib Symposium, Held in Maastricht, the Netherlands,
June 12–14, 2017, Springer International Publishing, Cham, 2018,
pp. 2057–2065.
[85] M.A.B. Promentilla, T. Sugiyama, T. Hitomi, N. Takeda, Quantification of
tortuosity in hardened cement pastes using synchrotron-based X-ray computed
microtomography, Cem. Concr. Res. 39 (2009) 548–557, https://doi.org/
10.1016/j.cemconres.2009.03.005.
[86] P. Panchmatia, J. Olek, N. Whiting, Electrical conductivity of concrete: the effects
of temperature, saturation and air content, Indian Concr. J. 89 (2015) 17–25.
[87] K.Y. Ann, S.I. Hong, Modeling chloride transport in concrete at pore and chloride
binding, ACI Mater. J. 115 (2018), https://doi.org/10.14359/51702194.
[88] N. Neithalath, J. Jain, Relating rapid chloride transport parameters of concretes
to microstructural features extracted from electrical impedance, Cem. Concr. Res.
40 (2010) 1041–1051, https://doi.org/10.1016/j.cemconres.2010.02.016.
[89] P. Yang, G. Sant, N. Neithalath, A refined, self-consistent Poisson-Nernst-Planck
(PNP) model for electrically induced transport of multiple ionic species through
concrete, Cem. Concr. Compos. 82 (2017) 80–94, https://doi.org/10.1016/j.
cemconcomp.2017.05.015.
[90] Y. Dhandapani, M. Santhanam, Investigation on the microstructure-related
characteristics to elucidate performance of composite cement with limestone-
calcined clay combination, Cem. Concr. Res. 129 (2020), 105959, https://doi.
org/10.1016/j.cemconres.2019.105959.
[91] G.A. Narsilio, R. Li, P. Pivonka, D.W. Smith, Comparative study of methods used
to estimate ionic diffusion coefficients using migration tests, Cem. Concr. Res. 37
(2007) 1152–1163, https://doi.org/10.1016/j.cemconres.2007.05.008.
[92] F.P. Glasser, J. Marchand, E. Samson, Durability of concrete — degradation
phenomena involving detrimental chemical reactions, Cem. Concr. Res. 38
(2008) 226–246, https://doi.org/10.1016/j.cemconres.2007.09.015.
K. De Weerdt et al.
[93] T. Sanchez, P. Henocq, O. Millet, A. Aït-Mokhtar, Coupling PhreeqC with electro-
diffusion tests for an accurate determination of the diffusion properties on
cementitious materials, J. Electroanal. Chem. 858 (2020), 113791, https://doi.
org/10.1016/j.jelechem.2019.113791.
[94] A. Vollpracht, B. Lothenbach, R. Snellings, J. Haufe, The pore solution of blended
cements: a review, Mater. Struct. 49 (2016) 3341–3367, https://doi.org/
10.1617/s11527-015-0724-1.
[95] G.K. Glass, N.R. Buenfeld, The presentation of the chloride threshold level for
corrosion of steel in concrete, Corros. Sci. 39 (1997) 1001–1013, https://doi.org/
10.1016/S0010-938X(97)00009-7.
[96] G. Sergi, G.K. Glass, A method of ranking the aggressive nature of chloride
contaminated concrete, Corros. Sci. 42 (2000) 2043–2049, https://doi.org/
10.1016/S0010-938X(00)00050-0.
[97] G. Sergi, S.W. Yu, C.L. Page, Diffusion of chloride and hydroxyl ions in
cementitious materials exposed to a saline environment, Mag. Concr. Res. 44
(1992) 63–69, https://doi.org/10.1680/macr.1992.44.158.63.
[98] J. Crank, The Mathematics of Diffusion, 2nd edition, Clarendon Press, 1979.
[99] O. Truc, J.P. Ollivier, L.O. Nilsson, Numerical simulation of multi-species
diffusion, Mater. Struct. 33 (2000) 566–573, https://doi.org/10.1007/
BF02480537.
[100] M. Geiker, E.P. Nielsen, D. Herfort, Prediction of chloride ingress and binding in
cement paste, Mater. Struct. 40 (2007) 405–417, https://doi.org/10.1617/
s11527-006-9148-2.
[101] J. Marchand, E. Samson, Predicting the service-life of concrete structures –
limitations of simplified models, Cem. Concr. Compos. 31 (2009) 515–521,
https://doi.org/10.1016/j.cemconcomp.2009.01.007.
[102] O.P. Kari, Y. Elakneswaran, T. Nawa, J. Puttonen, A model for a long-term
diffusion of multispecies in concrete based on ion–cement-hydrate interaction,
J. Mater. Sci. 48 (2013) 4243–4259, https://doi.org/10.1007/s10853-013-7239-
3.
[103] S. Pradelle, M. Thiéry, V. Baroghel-Bouny, Comparison of existing chloride
ingress models within concretes exposed to seawater, Mater. Struct. 49 (2016)
4497–4516, https://doi.org/10.1617/s11527-016-0803-y.
[104] V.Q. Tran, A. Soive, V. Baroghel-Bouny, Modelisation of chloride reactive
transport in concrete including thermodynamic equilibrium, kinetic control and
surface complexation, Cem. Concr. Res. 110 (2018) 70–85, https://doi.org/
10.1016/j.cemconres.2018.05.007.
[105] O.B. Isgor, W.J. Weiss, A nearly self-sufficient framework for modelling reactive-
transport processes in concrete, Mater. Struct. 52 (2019) 3, https://doi.org/
10.1617/s11527-018-1305-x.
[106] D. Conciatori, É. Grégoire, É. Samson, J. Marchand, L. Chouinard, Sensitivity of
chloride ingress modelling in concrete to input parameter variability, Mater.
Struct. 48 (2015) 3023–3036, https://doi.org/10.1617/s11527-014-0374-8.
[107] C. Andrade, Calculation of chloride diffusion coefficients in concrete from ionic
migration measurements, Cem. Concr. Res. 23 (1993) 724–742, https://doi.org/
10.1016/0008-8846(93)90023-3.
[108] O. Truc, J.P. Ollivier, M. Carcassès, A new way for determining the chloride
diffusion coefficient in concrete from steady state migration test, Cem. Concr. Res.
30 (2000) 217–226, https://doi.org/10.1016/S0008-8846(99)00232-X.
[109] E. Samson, J. Marchand, K.A. Snyder, Calculation of ionic diffusion coefficients
on the basis of migration test results, Mater. Struct. 36 (2003) 156–165, https://
doi.org/10.1007/BF02479554.
[110] fib, Model Code for Service Life Design, Fib Bulletin 34, CEB-FIB, 2006.
[111] fib, Fib Model Code for Concrete Structures 2010, Ernst & Sohn2013.
[112] ISO 16204, Durability — Service Life Design of Concrete Structures, 2012.
[113] S. Sui, F. Georget, H. Maraghechi, W. Sun, K. Scrivener, Towards a generic
approach to durability: factors affecting chloride transport in binary and ternary
cementitious materials, Cem. Concr. Res. 124 (2019), 105783, https://doi.org/
10.1016/j.cemconres.2019.105783.
[114] S. Fjendbo, H.E. Sørensen, K. De Weerdt, M.R. Geiker, The square root method for
chloride ingress prediction—applicability and limitations, Mater. Struct. 54
(2021) 61, https://doi.org/10.1617/s11527-021-01643-8.
[115] S.L. Poulsen, H. Sørensen, Chloride Ingress in Old Danish Bridges, 2nd
International Congress on Durability of Concrete (ICDC), New Dehli, India, 2014.
[116] S.L. Poulsen, H. Sørensen, U. Jönsson, Chloride ingress in concrete blocks at the
Rødbyhavn marine exposure site—status after 5 years, in: 4th International
Conference on Service Life Design for Infrastructures (SLD4), Delft, the
Netherlands, 2018.
[117] H. Justnes, M.O. Kim, S. Ng, X. Qian, Methodology of calculating required
chloride diffusion coefficient for intended service life as function of concrete
cover in reinforced marine structures, Cem. Concr. Compos. 73 (2016) 316–323,
https://doi.org/10.1016/j.cemconcomp.2016.08.006.
[118] V.G. Papadakis, C.G. Vayenas, M.N. Fardis, A reaction engineering approach to
the problem of concrete carbonation, AICHE J. 35 (1989) 1639–1650, https://
doi.org/10.1002/aic.690351008.
[119] A. Leemann, F. Moro, Carbonation of concrete: the role of CO2 concentration,
relative humidity and CO2 buffer capacity, Mater. Struct. 50 (2017) 30, https://
doi.org/10.1617/s11527-016-0917-2.
[120] V. Baroghel-Bouny, M. Dierkens, X. Wang, A. Soive, M. Saillio, M. Thiery,
B. Thauvin, Ageing and durability of concrete in lab and in field conditions:
investigation of chloride penetration, J. Sustain. Cement-Based Mater. 2 (2013)
67–110, https://doi.org/10.1080/21650373.2013.797938.
[121] O.M. Jensen, A.M. Coats, F.P. Glasser, Chloride ingress profiles measured by
electron probe micro analysis, Cem. Concr. Res. 26 (1996) 1695–1705, https://
doi.org/10.1016/S0008-8846(96)00158-5.
21
Cement and Concrete Research 173 (2023) 107287
[122] M. Khanzadeh Moradllo, B. Sudbrink, Q. Hu, M. Aboustait, B. Tabb, M.T. Ley, J.
M. Davis, Using micro X-ray fluorescence to image chloride profiles in concrete,
Cem. Concr. Res. 92 (2017) 128–141, https://doi.org/10.1016/j.
cemconres.2016.11.014.
[123] R. du Plooy, G. Villain, S. Palma Lopes, A. Ihamouten, X. Dérobert, B. Thauvin,
Electromagnetic non-destructive evaluation techniques for the monitoring of
water and chloride ingress into concrete: a comparative study, Mater. Struct. 48
(2015) 369–386, https://doi.org/10.1617/s11527-013-0189-z.
[124] K. Reichling, M. Raupach, N. Klitzsch, Determination of the distribution of
electrical resistivity in reinforced concrete structures using electrical resistivity
tomography, Mater. Corros. 66 (2015) 763–771, https://doi.org/10.1002/
maco.201407763.
[125] M. Fares, G. Villain, S. Bonnet, S. Palma Lopes, B. Thauvin, M. Thiery,
Determining chloride content profiles in concrete using an electrical resistivity
tomography device, Cem. Concr. Compos. 94 (2018) 315–326, https://doi.org/
10.1016/j.cemconcomp.2018.08.001.
[126] M. Torres-Luque, E. Bastidas-Arteaga, F. Schoefs, M. Sánchez-Silva, J.F. Osma,
Non-destructive methods for measuring chloride ingress into concrete: state-of-
the-art and future challenges, Constr. Build. Mater. 68 (2014) 68–81, https://doi.
org/10.1016/j.conbuildmat.2014.06.009.
[127] Y. Seguí Femenias, U. Angst, F. Caruso, B. Elsener, Ag/AgCl ion-selective
electrodes in neutral and alkaline environments containing interfering ions,
Mater. Struct. 49 (2016) 2637–2651, https://doi.org/10.1617/s11527-015-0673-
8.
[128] P.S. Mangat, B.T. Molloy, Prediction of long term chloride concentration in
concrete, Mater. Struct. 27 (1994) 338–346, https://doi.org/10.1007/
BF02473426.
[129] K. Stanish, M. Thomas, The use of bulk diffusion tests to establish time-dependent
concrete chloride diffusion coefficients, Cem. Concr. Res. 33 (2003) 55–62,
https://doi.org/10.1016/S0008-8846(02)00925-0.
[130] D. Boubitsas, L. Tang, P. Utgenannt, Chloride Ingress in Concrete Exposed to
Marine Environment -Field Data up to 20 Years’ Exposure, SP Swedish National
Testing and Research Institute, 2014.
[131] S. Engelund, General Guidelines for Durability Design and Redesign, vol 15 of
Document BE95–1347/R, DuraCrete: Probabilistic performance based durability
design of concrete structures, European Union Brite EuRam III, CUR, Gouda,
Netherlands, 2000.
[132] F. Georget, J.H. Prévost, B. Huet, Reactive transport modelling of cement paste
leaching in brines, Cem. Concr. Res. 111 (2018) 183–196, https://doi.org/
10.1016/j.cemconres.2018.05.015.
[133] F. Georget, J.H. Prévost, B. Huet, Impact of the microstructure model on coupled
simulation of drying and accelerated carbonation, Cem. Concr. Res. 104 (2018)
1–12, https://doi.org/10.1016/j.cemconres.2017.11.008.
[134] M.B. Clennell, Tortuosity: a guide through the maze, Geol. Soc. Lond., Spec. Publ.
122 (1997) 299–344, https://doi.org/10.1144/GSL.SP.1997.122.01.18.
[135] S. Chatterji, Transportation of ions through cement based materials. Part 1
fundamental equations and basic measurement techniques, Cem. Concr. Res. 24
(1994) 907–912, https://doi.org/10.1016/0008-8846(94)90010-8.
[136] E. Samson, J. Marchand, J.J. Beaudoin, Describing ion diffusion mechanisms in
cement-based materials using the homogenization technique, Cem. Concr. Res. 29
(1999) 1341–1345, https://doi.org/10.1016/S0008-8846(99)00101-5.
[137] S. Torquato, Random Heterogeneous Materials: Microstructure and Macroscopic
Properties, Springer-Verlag, 2002.
[138] B. Bary, A polydispersed particle system representation of the porosity for non-
saturated cementitious materials, Cem. Concr. Res. 36 (2006) 2061–2073,
https://doi.org/10.1016/j.cemconres.2006.07.001.
[139] E. Stora, B. Bary, Q.-C. He, On estimating the effective diffusive properties of
hardened cement pastes, Transp. Porous Media 73 (2008) 279–295, https://doi.
org/10.1007/s11242-007-9170-z.
[140] K. Bourbatache, O. Millet, A. Aït-Mokhtar, O. Amiri, Modeling the chlorides
transport in cementitious materials by periodic homogenization, Transp. Porous
Media 94 (2012) 437–459, https://doi.org/10.1007/s11242-012-0013-1.
[141] R.A. Patel, Q.T. Phung, S.C. Seetharam, J. Perko, D. Jacques, N. Maes, G. De
Schutter, G. Ye, K. Van Breugel, Diffusivity of saturated ordinary Portland
cement-based materials: a critical review of experimental and analytical
modelling approaches, Cem. Concr. Res. 90 (2016) 52–72, https://doi.org/
10.1016/j.cemconres.2016.09.015.
[142] A.T. Horne, I.G. Richardson, R.M.D. Brydson, Quantitative analysis of the
microstructure of interfaces in steel reinforced concrete, Cem. Concr. Res. 37
(2007) 1613–1623, https://doi.org/10.1016/j.cemconres.2007.08.026.
[143] A. Leemann, R. Loser, B. Münch, Influence of cement type on ITZ porosity and
chloride resistance of self-compacting concrete, Cem. Concr. Compos. 32 (2010)
116–120, https://doi.org/10.1016/j.cemconcomp.2009.11.007.
[144] H.S. Wong, M. Zobel, N.R. Buenfeld, R.W. Zimmerman, Influence of the
interfacial transition zone and microcracking on the diffusivity, permeability and
sorptivity of cement-based materials after drying, Mag. Concr. Res. 61 (2009)
571–589, https://doi.org/10.1680/macr.2008.61.8.571.
[145] Z. Wu, H.S. Wong, N.R. Buenfeld, Influence of drying-induced microcracking and
related size effects on mass transport properties of concrete, Cem. Concr. Res. 68
(2015) 35–48, https://doi.org/10.1016/j.cemconres.2014.10.018.
[146] A.C.A. Muller, K.L. Scrivener, A.M. Gajewicz, P.J. McDonald, Densification of
C–S–H measured by 1H NMR relaxometry, J. Phys. Chem. 117 (2013) 403–412,
https://doi.org/10.1021/jp3102964.
[147] E. Berodier, J. Bizzozero, A. Muller, Mercury intrusion Porosimetry, in:
K. Scrivener, R. Snellings, B. Lothenbach (Eds.), A Practical Guide to
K. De Weerdt et al.
Microstructural Analysis of Cementitious Materials, CRC Press, 2016,
pp. 419–444.
[148] H. Ranaivomanana, J. Verdier, A. Sellier, X. Bourbon, Prediction of relative
permeabilities and water vapor diffusion reduction factor for cement-based
materials, Cem. Concr. Res. 48 (2013) 53–63, https://doi.org/10.1016/j.
cemconres.2013.02.008.
22
Cement and Concrete Research 173 (2023) 107287
[149] K. Scrivener, T. Matschei, F. Georget, P. Juilland, A. Kunhi-Mohammed,
Hydration and Thermodynamics, ICCC Bangkok, Cement and Concrete Research
Special Issue, 2023 (submitted 2023).
[150] U.M. Angst, O.B. Isgor, C.M. Hansson, A. Sagüés, M.R. Geiker, Beyond the
chloride threshold concept for predicting corrosion of steel in concrete, Appl.
Phys. Rev. 9 (2022), 011321, https://doi.org/10.1063/5.0076320.