Nuclear Engineering and Design 237 (2007) 20832089

Chemo-mechanical coupling behaviour of leached concrete

Part I: Experimental results
V.H. Nguyen a , H. Colina b , J.M. Torrenti c,d, , C. Boulay c , B. Nedjar a
a

Laboratoire dAnalyse des Materiaux et Identication, Ecole Nationale des Ponts et Chaussees,
Institut Navier, 6 et 8, Avenue Blaise Pascal, 77455 Marne la Vallee Cedex 2, France
b ATILH, 7, Place de la D
efense, 92974 Paris-La-Defense Cedex, France
c LCPC Paris, 58, Boulevard Lefebvre 75732 Paris Cedex 15, France
d LMT, ENS Cachan, 61, Avenue du Pr
esident Wilson, 94235 Cachan, France
Received 10 April 2006; received in revised form 5 February 2007; accepted 14 February 2007

Abstract
This paper deals with concrete behaviour under chemical and mechanical degradations. Experimental investigations are described where the
effects of the calcium leaching process of concrete on its mechanical properties are highlighted. The calcium leaching and mechanical tests on
cement paste, mortar and concrete samples are presented. Because of the slow kinetics of leaching under deionised water, an accelerated method has
been chosen by using an ammonium nitrate solution instead. The specimens are immersed into a 6 mol/l ammonium nitrate solution with a controlled
pH disposal. To quantify the leaching evolution, the degradation depth is then measured at certain time intervals by means of a phenolphthalein
solution. The experimental results show the chemical degradation of the cement-based material and the important role of aggregate in the calcium
leaching process of concrete. Compression tests of concrete samples are also performed. We observe that there is a strong coupling between the
calcium leaching and the mechanical behaviour; as leaching grows, a loss of stiffness and of strength are observed and a smoother post-peak
behaviour is noted.
2007 Elsevier B.V. All rights reserved.

1. Introduction
Durability will certainly be the key in future use of concrete in long-term structural applications. In the long term, the
durability of concrete is not exclusively affected by damage
induced by mechanical loads. The lifetime of such a material
may also depend on the environment. As a typical example,
concrete is commonly employed in radioactive waste disposal
and concrete containment structures that must therefore ensure
the load-bearing capacity over extended periods depending on
the level of radioactivity. In the lifetime of nuclear waste, the
scenario of concrete degradation is calcium leaching due to onsite water. This leaching implies an increase in porosity, and
modification of the microstructure of concrete which, amongst
other things, influences the mechanical behaviour.

DOI of original article:10.1016/j.nucengdes.2007.02.012.

Corresponding author at: LCPC Paris, 58, Boulevard Lefebvre 75732 Paris
Cedex 15, France. Tel.: +33 1 40 43 54 40; fax: +33 1 40 43 65 20.
E-mail address: jean-michel.torrenti@ponts.org (J.M. Torrenti).

0029-5493/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.nucengdes.2007.02.013

The calcium leaching of the cementitious material is controlled by the chemical equilibrium of the hydration production.
It depends on two main consecutive phenomena with different
kinetics (see Torrenti et al., 1999):
material transport by diffusion, resulting from concentration
gradients between the solid interstitial solution and the aggressive environment outside the cement samples;
dissolutionprecipitation chemical reactions induced by the
concentration variations brought about by diffusion.
The leaching process begins with a total dissolution of
portlandite, then ettringite and followed by a progressive decalcification of C-S-H phase. Several authors have researched
the chemical degradation on cement paste and mortar also
(Adenot, 1992; Bourdette, 1994; Carde et al., 1996; Gerard,
1996; Tognazzi, 1998; Le Bellego, 2001; Ulm et al., 2003)
among many other references. Experimental data reveal that the
leaching process timescale is governed by the diffusion process,
as the dissolution is much faster, i.e. the leaching fluxes are

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imposed by diffusion. In the solid phase assemblage, a sharp

leaching front is observed experimentally. These fronts separate
zones where mineralogy is constant (Adenot, 1992). Experiments also show that the leaching fluxes and the position of
the degradation front are proportional to the square root of time
(Carde et al., 1996; Tognazzi, 1998; Torrenti et al., 1998), which
agrees with theoretical considerations (Mainguy and Coussy,
2000).
Natural leaching is a very slow process (a few centimetres per
hundred years). For laboratory experiments, the use of deionised
water is not an optimum choice for concrete for which we need
several centimetres of degradation. Accelerated leaching is necessary to leach the samples in a reasonable time. There are three
principal ways to accelerate calcium leaching: using temperature (Kamali, 2003), using an electrical field (Saito et al., 1992;
Gerard, 1996) and by replacing deionised water with a different solution agent to increase concentration gradients between
the interstitial solution and the aggressive environment. The
majority of the experiments on calcium leaching of cementitious material samples are performed by using the last method.
The deionised water is replaced by a strongly concentrated
ammonium nitrate solution (Goncalves and Rodrigues, 1991;
Carde et al., 1996; Carde and Francois, 1997; Gerard, 1996;
Tognazzi, 1998; Le Bellego, 2001; Ulm et al., 2003; Kamali,
2003).
The influence of calcium leaching on the mechanical
behaviour of the cement paste and mortar has been investigated
by several authors (Carde et al., 1996; Ulm et al., 1999; Le
Bellego et al., 2001; Heukamp et al., 2001). In their analysis
of the experimental results, Carde et al. (1996) show that the
stiffness of the material specimens is significantly reduced after
the total dissolution of portlandite and the progressive dissolution of C-S-H. Both mechanical and water porosity tests show
a linear variation between the loss of strength and the growth
in porosity in relation to the ratio between the degraded and the
sound cross-sections. Compared with the sound material, the
ductility of the chemically degraded material is larger because
the microstructure is modified. The influence of the chemical
degradation on mechanical behaviour has been presented by a
relation between the calcium concentration in solid phase and
the elasticity modulus, as in (Gerard, 1996) or the strength as in
(Torrenti et al., 1998) by using micro-hardness experiments. Le
Bellego (2001) has shown recently that the mechanical properties of mortar decrease as leaching grows. For degradation ratios
equal to 48, 59 and 74%, the loss of stiffness of mortar specimens is about 23, 36 and 53%, respectively. From triaxial tests
of cement specimens subjected to accelerated leaching, a strong
dependence of the mechanical properties on the pore pressure
due to the increased pore space and the reduction of the materials frictional performance of the leached cement paste is noted,
see (Heukamp et al., 2001, 2003). However, experimental result
for calcium leaching of concrete and post-peak behaviour of
concrete leached are not yet available in literature data. The differences between cement paste or mortar and concrete (cement
content, size of aggregates, . . .) should influence the leaching
process and the mechanical behaviour of the leached concrete
in the pre and post-peak regimes.

The paper is organised as follows. In Section 2, we outline

the experimental setup and results on cement paste, mortar and
concrete specimens. In Section 3, the mechanical properties of
concrete are investigated on cylindrical concrete samples subjected to uniaxial compression tests after accelerated leaching.
The mean stressmean strain diagrams at different degradation
levels are presented. Finally, the conclusions and perspectives
are drawn in Section 4.
2. Design and setup of the accelerated leaching
procedure
The aim of the experimental campaign is to determine the
calcium leaching kinetic of the cementitious phase at different
scales (cement paste, mortar and concrete). It allows to observe
the influence of the aggregate on the calcium leaching of concrete. This section presents design considerations for the calcium
leaching device and its practical application and results.
2.1. Materials and samples
The concrete was composed of siliceous aggregates and
an OPC cement (CEM 1 52,5). The composition of concrete
used is presented in Table 1, where the ratio between the concrete components is: cement:sand:gravel = 1:1.82:2.8, with a
watercement ratio of 0.6. The cement paste has the same
watercement ratio equal to 0.6 and the ratio between the mortar
components is: water:cement:sand = 0.6:1:1.82.
In our experimental program, the samples used for the case
of cement paste and mortar are cylinders 32 mm diameter and
100 mm high. Two types of specimens are used for concrete:
full cylinders with dimensions 110 mm 220 mm and hollow
cylinders with the same external dimensions and a centred hole
of diameter = 27 mm. The top and the bottom of the concrete
samples was protected from leaching by means of a silicon resin
in order to have only leaching in the central part of the samples
and not at the level of loaded surfaces.
2.2. Realisation of the calcium leaching process
In this study, a degradation under ammonium nitrate solution
has been used. The equivalence of the leaching process under
deionised water and under ammonium nitrate solution is highlighted experimentally by Carde et al. (1996), Tognazzi (1998).
The degraded state of specimens may be determined easily by
using the pH indicators.
Table 1
Composition of a 1 m3 of concrete
Components

Quantity (kg)

Siliceous sand S28 (0.20.5 mm)

Siliceous sand S30 (0.41.0 mm)
Siliceous sand S36 (1.03.15 mm)
Crotoy siliceous gravel (4.012.5 mm)
Cement CEM I
Water

281
193
210
1050
375
225

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Table 2
Experimental results of chemical degradation of limestone
Length (cm)

Diameter (cm)

Sound state
0.79
2.85
After 142 days of degradation
0.60
2.70

Fig. 1. Scheme of the calcium leaching test of concrete under 6 M ammonium

nitrate solution.

After 5 months of curing (water storage), the specimens were

immersed in an ammonium nitrate solution with a concentration
equal to 6 mol/l (6 M). The experimental setup for accelerated
calcium leaching is presented in Fig. 1. The pH and temperature
are recorded by an acquisition system. The volume of solution
was chosen to avoid renewal: while pH is lower than 8.2 we can
avoid renewing (Le Bellego, 2001). Knowing the quantity of
calcium that would be leached we can estimate the quantity of
ammonium nitrate we need to respect this condition. The leaching process results from the high gradients of concentrations
between the pore solution in the cement paste and the aggressive solution that surrounds the samples. These gradients then
induce a diffusion process of the calcium present in the pore
solution towards the environment. Subsequently, at each period
of time (36, 57, 105, 152, 163, 197, 274 and 547 days for the case
of concrete), specimens were extracted to measure the depth of
the chemical degradation and test their mechanical behaviour.

Weight (g)

Porosity

2.70

28.6

1.40

32.3

degradation, we show that the specimens of limestone have a

limited increase in porosity and mainly a significant reduction
in volume and mass (see Table 2 and Fig. 2).
This result shows that limestone is unstable in the ammonium nitrate solution. This explains the choice to use siliceous
aggregates for our tests. For real storage structures limestone
will be stable, because on-site water contains sufficient quantities of calcium. Calcareous aggregates could therefore be used
instead of siliceous ones for nuclear waste storage.
The degraded depth is determined by using the phenolphthalein on sectioned samples. The pH value in the pore solution
of cementitious materials is higher than 12.5, creating a very
basic environment. Consequently, an ammonium nitrate solution
with pH values below this level characterises the acid environment. We can use the pH indicator like phenolphthalein to
distinguish between the sound zone and the degraded zone. Phenolphthalein turns from colourless in acidic solutions to pink
in basic solutions with the transition occurring around pH 9.
However, the dissolution of portlandite occurs as long as the
pH values drop below 12. Therefore, phenolphthalein does not
give the exact position of the dissolution front of portlandite.
However, by comparison between the measurement by phenolphthalein and by SIMS microprobe analysis (Le Bellego,
2001) has shown that for the cement paste the total degraded
depth et can be determined by correcting the degraded depth
ephenol measured by phenolphthalein with the formula:

2.3. Results

et = 1.17 ephenol

To avoid alkali-aggregate reaction, limestone aggregates are

planed to be used for concrete in the case of nuclear waste storage. But limestone could be leached in our solution. That is why
we present firstly the result of the chemical degradation of limestone. This experiment has been performed to characterise the
leaching properties of limestone as well as to check the technique used and precautions for the later test. After 142 days of

In the cross-section of the specimens, two distinct zones may

be observed: a sound zone, i.e. with the pink colour caused by
the phenolphthalein solution, and a degraded zone, i.e. with the
grey colour (see Figs. 39).
The thickness of this degraded zone can be measured by using
the measurements at 16 points around the specimen. The total
degraded depth is the mean of these measurements.

Fig. 2. Photo of the limestone sample on the sound state and after 142 days of degradation.

(1)

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V.H. Nguyen et al. / Nuclear Engineering and Design 237 (2007) 20832089

Fig. 3. Degradation state of the cement cylinder after 14 days. The pH indicator
is phenolphthalein (pink when pH > 12.5). (For interpretation of the references
to colour in this figure legend, the reader is referred to the web version of the
article.)

Fig. 5. Degradation state of the concrete hollow cylinder after 36 days.

The relation
between the degraded depth and the square root

of time t shows a linear evolution for the three cases (cement

paste, mortar and concrete) (see Figs. 10 and 11). This means
that the kinetics of the chemical degradation of the cementitious
material is governed by a diffusion process and can be described
using Ficks law.
Comparing the results obtained with cement paste and mortar, it is interesting to note that the degraded depth evolutions are
almost the same for the two cases. A comparison of these results
and the experimental results of concrete highlights a significant
difference. For example, after 25 days of degradation, the difference between the degraded depth in concrete and mortar is about
15% (see Figs. 10 and 11). These results highlight the influence
of the aggregates in concrete. Its volume fraction and morphological geometries obviously play an important role. This effect

Fig. 6. Degradation state of the concrete full cylinder after 36 days.

Fig. 4. Degradation state of the mortar cylinder after 14 days.

Fig. 7. Degradation state of the concrete hollow cylinder after 197 days.

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Fig. 8. Degradation state of the concrete full cylinder after 197 days.

is accounted for by using the homogenisation method (Nguyen

et al., 2006).
Comparing the results obtained with full and hollow cylinder,
we note that the external degraded depth is the same. But the
internal degraded depth of the hollow cylinder is lower than the
external. This seems to be due to a different boundary condition
in the hole: the calcium concentration should be higher (it was
not possible to check this assumption).

Fig. 10. Degraded depth evolution vs. the square root of time for the cement
paste and mortar specimens.

3. Mechanical behaviour of leached concrete

the stiffness, the mean strength, the complete mean stressmean

strain curves and irreversible deformations.

3.1. Experimental setup

3.2. Results

At each time interval of the chemical degradation, concrete

specimens are subjected to compression tests in order to measure
the complete mean stressmean strain curve, the mean stiffness
and strength. The device used is a MFL-5000 press with a maximum capacity of 5000 kN. An extensometer and three LVDT
placed between the platens are used (see Fig. 12). The extensometer is clamped directly on the specimen and measures the
displacement of the central part of the sample on a 110 mm
base length (Boulay and Colson, 1981). The mean value of the
three LVDT is used to control the test. Loading is controlled by
this displacement between the platens with cycles to determine

The mean strain is the relative variation of the base length l0 of

the extensometer (110 mm). This is only a mean strain because
of the localisation process in the softening range (Torrenti et al.,
1993).
The mean compressive stress is evaluated by dividing the
load F by the area of the cross-section of specimen S. It is a mean
stress because, due to the heterogeneity of the chemical degra-

Fig. 9. Degradation state of the concrete hollow cylinder after 163 days.

Fig. 11. Degraded depth evolution vs. the square root of time for the concrete
specimens.

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V.H. Nguyen et al. / Nuclear Engineering and Design 237 (2007) 20832089

Fig. 12. Experimental setup for the compressive test of concrete.

dation, we have different local mechanical properties (Youngs

modulus for instance) conducting to different local stresses in
the samples.
We observe that the mean stiffness and the mean compressive
strength decrease with the degradation time until values corresponding to a totally degraded concrete are stabilised. As found
by (Ulm et al., 2002), we observe residual strength and Youngs
modulus. Figs. 13 and 14 illustrate these evolutions.
In addition, and by way of illustration, the results of the compression tests for the hollow cylinders at different degradation
times are shown in Fig. 15. We note that there is a strong coupling
between the calcium leaching and the mechanical behaviour.
The sound concrete has an almost brittle behaviour, while as the
leaching grows, concrete becomes more and more ductile with
important strains: the mean strain at peak stress is almost three
times higher when concrete is totally leached. Similar results
were obtained by (Le Bellego, 2001) with mortar.
In the case of cyclic loading, the experimental results reveal
the existence of inelastic deformations (see Figs. 16 and 17).
These deformations are larger with the leaching time. There is
an evolution when concrete is leached towards a more plastic
material. This is coherent with Heukamps results who have

Fig. 13. Evolution of the mean stiffness vs. the degradation time for full and
hollow cylinders.

Fig. 14. Evolution of the strength vs. the degradation time for full and hollow
cylinders.

Fig. 15. Mean stress vs. mean strain curves at different degradation times (hollow cylinders).

shown that leached C-S-H is a cohesive incompressible material and that the pores created by the calcium leaching provides
space for the incompressible solid during compressive loading
(Heukamp et al., 2003).
Eventually, one should note that in only two cases our
tests could be considered homogeneous: for plain concrete
and for totally leached concrete. In these cases, the constitu-

Fig. 16. Mean stress vs. mean strain curves under cyclic loading after 197 days
of degradation (hollow cylinders).

V.H. Nguyen et al. / Nuclear Engineering and Design 237 (2007) 20832089

Fig. 17. Means stress vs. means strain curves under cyclic loading after 679
days of degradation (hollow cylinders).

tive behaviour could be obtained directly from the test. For all
intermediate states, an inverse analysis that take into account a
non-homogeneous degraded state should be considered.
4. Conclusions
We have presented an experimental program of the chemomechanical behaviour of leached concrete. Calcium leaching
test on cement paste, mortar and concrete highlighted the kinetics of calcium leaching of cementitious materials and have
shown clearly the important role of aggregates on the leaching
process of concrete. The mechanical tests show the chemomechanical behaviour of leached concrete: there is a strong
coupling between the calcium leaching and the mechanical
behaviour. As leaching grows, a loss of strength and stiffness
is observed, and a smoother post-peak behaviour with increasing irreversible straining is to be noted. Cyclic loading suggests
a plastic-like constitutive behaviour for the completely leached
concrete.
Acknowledgement
Financial support for this research was provided by the
ENPC-IRSN collaboration under project no. IRSN/2002-03827.
This support is gratefully acknowledged.
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