Materials Today Communications 35 (2023) 105750

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Materials Today Communications

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

Prediction of diffusion properties of cement-based materials incorporating

recycled rubber aggregates: Effect of microstructure on macro diffusion
properties
A. Abou-Chakra a ,∗, G. Blanc b , A. Turatsinze a , G. Escadeillas a
a
LMDC, Université de Toulouse, INSA, UPS Génie Civil, 135 Avenue de Rangueil, Toulouse Cedex 04, 31077, France
b Ménard, Nozay 91620, France

ARTICLE INFO ABSTRACT

Keywords: In recent years, significant progress has been made in the development of new, eco-friendly, cement-based
Cement-based materials materials. However, predicting their durability from the new material composition is still a challenging
Rubber recycled aggregates task. There have been very few studies of micromechanical models based on micro-geometric features on
Eco-friendly
cement-based materials incorporating recycled rubber aggregates. In this context, a multiscale model using
Diffusion properties
the microstructural characteristics is proposed to predict their diffusion properties. After the description of the
Interface transition zone
Homogenization schemes
physically-based approach, its accuracy is evaluated by comparing the model predictions with experimental
results from mortars with different types of aggregates (natural sand and rubber). In the study, it is assumed
that diffusion of ionic species occurs primarily through the porous network of the cement matrix, but also
takes place at the matrix-aggregate interface transition zone (ITZ). The method used for modelling is based
on homogenization schemes and the spherical n-phase inclusion model which allow the ITZ to be taken into
account.

1. Introduction in an aggressive environment, the diffusion coefficient is considered

In recent years, significant progress has been made in the de-
velopment of new, eco-friendly, cement-based materials. The use of
recycled aggregates from waste in concrete can offer the opportunity
to, at the same time, protect the environment and save our resources.
Many alternatives such as recycled concrete aggregates (RCA), widely
studied in recent decades (i.e.[1] and the recent reviews [2,3]), have
been used in building materials. Incorporating rubber aggregates by
grinding end-of-life tyres provides also an opportunity to recycle rubber
tyres, thus helping to meet the demand of a clean environment by
recycling end-of-life tyres ([4,5]). The impact of rubber aggregates
in concrete formulation and their effect on its mechanical properties
was studied in [6]. Nevertheless, the effect of the new formulation
on its durability remains a key challenge, especially its performance
prediction. Degradation phenomenon being linked to the ingress of
aggressive agents into the composites, the prediction of their diffusive
properties is crucial to assess the risks involved by the addition of such
aggregates into the composites.
The diffusion properties of these materials seem essential if the
kinetics of degradation is to be predicted. Moreover, among some
material properties to predict the durability of a cement-based material
as a durability indicator (DI) [7,8]. The development of analytical
formulas to assess the diffusion of cement-based materials exposed in an
aggressive environment seen as a durability parameter. This can help to
predict the service life of concrete and improve the performance-based
criteria (specifications) related to the DIs [7].
In the literature, diffusion of ionic species is mainly analysed
through two phenomena: the diffusion of chloride ions in the case of
reinforcement corrosion and the diffusion of calcium ions in the case
of leaching. Few studies are related to the diffusion of sulphate inside
the porous network during a sulphate attack.
Concerning chloride attack, studies by Atkinson and Nickerson [9]
or Hobbs and Matthews [10] used an empirical relationship linking the
diffusion coefficient of chloride ions with the water to cement ratio
(W/C) of the cementitious material, exposed to a marine environment.
According to Hobbs [11], the diffusion coefficient of chloride ions in
concrete depends on the W/C ratio. But the correlation between these
two parameters is less strong for a concrete than for a cement paste,
which again shows the non-negligible influence of the granular skeleton
distribution in a cementitious material.
The analysis and prediction of the leaching of cementitious mate-
rials over the long term have also been the subject of many studies.

∗ Corresponding author.
E-mail address: abouchak@insa-toulouse.fr (A. Abou-Chakra).

https://doi.org/10.1016/j.mtcomm.2023.105750
Received 13 May 2022; Received in revised form 10 February 2023; Accepted 3 March 2023
Available online 6 March 2023
2352-4928/© 2023 Published by Elsevier Ltd.
A. Abou-Chakra et al.
Tognazzi [12] proposes an empirical relation that exponentially links
the diffusion coefficient of calcium ions Dca and the porosity of healthy
material 𝜙 in the case of cement pastes. The values of the diffusion
parameters are available in the works of Mainguy and al. [13] for a
CEM I cement. It is noteworthy that results from this model are in good
agreement with experimental ones from the work of Adenot [14] and
Richet and al. [15].
However, this conclusion is limited to paste. Therefore, a general
diffusion equation for a cement-based material is required and it must
take the presence of aggregates into account. While representing a
non-porous volume with no diffusion phenomenon, aggregates affect
the diffusion inside the material through the interfacial transition zone
(ITZ), which shows higher porosity than that of the cement paste. The
ITZ is known to be a weaker area and larger porosity influencing the
permeability or the diffusive properties of the material (see [16]). It is
then essential to be considered and its effect on the durability of the
material has to be studied.
Regarding the specific case of rubber aggregates in cementitious
materials characterized by a weak ITZ, there is no consensus among
researchers on the diffusion properties of this material, making the
prediction of these properties even more crucial. From [17–19], the co-
efficient of chloride diffusion can either decrease or increase depending
on many parameters such as rubber type and size, concrete type, the
replacement and the w/c ratios. Compared to empirical models, the
choice made in this paper is to use a multi-scale modelling based on
the physics of the material from the description of the microstructure
and phase properties. For the prediction of the diffusion of mortars
and cements, an important development on multi-scale modelling has
been made with two strategies, the analytical modelling and the nu-
merical computation. The software codes CEMHYD3D by Bentz and
Garboczi [20] or HYMOSTRUC3D hydration simulation model by K.
Van Breugel [21] model the cement hydration and lead to the studies
of the diffusion transport through cement paste by Garboczi et al. [22]
and Liu et al. [23]. These computational models are mostly used
at the scale of the cement paste and are computationally costly to
model the transport from the cement paste to the upper scale of the
mortar. An alternative way is the analytical homogenization schemes
within the framework of micromechanics and using Eshelby-based
homogenization techniques. Bary et al. [24,25] develop a multi-scale
homogenization of the diffusion properties of cement paste. Achour
et al. [26] extended this work on the both transport and mechanical
properties of Portland cement. Yang et al. [27] provide a multi-scale
modelling of the transport properties in cement-based materials. Nev-
ertheless, studies on one hand multi-reinforced materials containing
recycled rubber inclusions and on the other hand their corresponding
ITZs are scarce. The prediction of the diffusion of mortar containing
sand and lightweight aggregates, such as rubber aggregates, remains
open and makes it impossible to use the existing empirical relations
recalled here. In this context, micro-mechanical theory appears useful
to propose a macroscopic law governing the diffusion of a composite
material when the properties and volume fractions of each phase are
known.
The main objective of this paper is then to predict the durability
of cement-based composite exposed to an aggressive environment ,
where a proportion of natural sand is replaced by rubber aggregates
from recycled used tyres. This paper focuses on a constitutive model
predicting diffusion coefficients of matrix-inclusion composites and
enabling their accuracy to be evaluated. This is done by comparing the
model predictions with experimental tests on mortars using different
types of aggregate (natural sand and rubber). The diffusion of ionic
species occurs primarily through the porous network of the cement
matrix, but also through the ITZ. The method used for modelling is
based on standard homogenization schemes (Mori–Tanaka [28] and
self-consistent [29] estimations, noted (MT) and (SC) respectively in
the following) and on the spherical n-phase inclusion model published
by Hervé and Zaoui [30] allowing the ITZ to be considered. A similar
2
Materials Today Communications 35 (2023) 105750
approach was adopted by [31] but for the prediction of mechanical
properties. However, most of the studies previously referenced [24,25]
consider a direct application of the n-sphere model from [30] which as-
sumes one type of aggregates as a core surrounded by n-layer spherical
inclusions embedded in the effective medium, it means the morphology
of the SC estimate. The model is applied in this paper and extended
to the MT estimate thanks to the determination of the corresponding
localization tensors. Moreover, the extended MT and SC estimates, in
contrast with the n-sphere model [30], can now be applied to mortars
with more than one type of aggregates and give predictions of mortars
containing new type of aggregates by substitution of a part of natural
sand. The novelty of this article is then to focus on new types of
cementitious material, eco-friendly mortars containing different rates of
rubber tyre waste aggregates, and also as part of the validation process
a second type of mixes containing light-weight aggregates, expanded
clay.
2. Macroscopic diffusion coefficient
The goal is to solve the diffusion problem for a chemical species in
a heterogeneous medium through the use of classical homogenization
schemes. Let us consider a uniform concentration gradient 𝑐|∞ = 𝐻 ⋅ 𝑧
as the boundary condition of the representative volume element (RVE)
domain 𝛺 where 𝐻 is the macroscopic concentration gradient and
𝑧 ∈ 𝜕𝛺. At the micro level, the transport description is based on
the principle of mass conservation and diffusive mass flow. In each
phase 𝛺𝑘 , the ion volume gradient is a linear function of 𝐻 through
a localization tensor A as follows:
⟨ ⟩
𝑔𝑟𝑎𝑑 𝑐 = A𝑘 ⋅ 𝐻 (1)
𝛺𝑘
The macroscopic mass flux can be obtained by homogenizing the
microscopic flux of diffusion 𝑗 on the 𝛺 domain:
⟨ ⟩
𝐽= 𝑗 = −Dℎ𝑜𝑚 ⋅ 𝐻 (2)
𝛺
where Dℎ𝑜𝑚 is the homogenized macroscopic diffusion tensor. If we
consider an isotropic case, A𝑘 = 𝐴𝑘 I, then Dℎ𝑜𝑚 = 𝐷ℎ𝑜𝑚 I and:
∑
𝐷ℎ𝑜𝑚 = 𝜙𝑘 𝐷𝑘 𝐴𝑘 (3)
𝑘
where 𝜙𝑘 corresponds to the volume fraction of the phase 𝑘 in the
material considered.
According to relation (3), characterizing the homogenized diffusion
coefficient of the material depends on the determination of the localiza-
tion tensors 𝐴𝑘 . As it is difficult to calculate these tensors exactly, the
following estimations obtained from standard homogenization schemes
are used: Mori–Tanaka [28] and self-consistent [29] estimations that
are noted MT and SC respectively in the following.
The MT estimation considers an ellipsoidal inclusion embedded in
an infinite medium subjected to a homogeneous gradient 𝑐 = 𝐻 0 ⋅ 𝑧.
Relation (1) thus becomes:
⟨ ⟩
𝑔𝑟𝑎𝑑𝑐 = 𝐴0𝑘 ⋅ 𝐻 0 (4)
𝛺𝑘
and then:
( )−1
∑ ∑
𝐷ℎ𝑜𝑚 = 𝜙𝑘 𝐷𝑘 𝐴0𝑘 ⋅ 𝐴0𝑠 (5)
𝑘 𝑠
Now, if the self-consistent estimation is considered, inclusions are em-
bedded in an infinite medium with the diffusive properties of the equiv-
alent homogeneous medium: 𝐷ℎ𝑜𝑚 . This is the case of the n-layered
model detailed in [32].
For the simple case of a two-phase porous medium made up of solid
(𝐷𝑠 = 0) and liquid (𝐷𝑙 ), the homogenized diffusion coefficient can be
estimated as follows (see [33]):
A. Abou-Chakra et al. Materials Today Communications 35 (2023) 105750

• the Mori–Tanaka scheme gives:

2𝜙
𝐷ℎ𝑜𝑚 = 𝐷 (6)
3−𝜙 𝑙

• and the self-consistent one:

3𝜙 − 1
𝐷ℎ𝑜𝑚 = 𝐷𝑙 , (𝜙 ≥ 1∕3) (7)
2
where 𝜙 is the pore volume fraction. At this point some remarks can
be made:

• The equations are given for the simple case of spherical solid
inclusions. In the more complex case of ellipsoidal inclusions, the
diffusion coefficient is influenced by the orientation of particles
and then the deviation of the path in the pore network making
Fig. 1. 2-layered spherical inclusion embedded in an infinite matrix.
the geometrical concept of tortuosity relevant [34].
• The equations Eqs. (6) and (7) obtained from MT and SC schemes
are very different.
The first gives a strictly positive and concave relationship be- The n-sphere composite representation [25,32] is used to determine
tween diffusion coefficient and porosity. The considered morphol- the localization tensor of each phase.
ogy is a matrix-inclusion morphology in which the fluid surrounds In this model, a composite of 2-isotropic concentric spheres embed-
the solid inclusions. ded in an infinite phase 3 is considered. Phase 1 constitutes the central
The second equation vanishes for a porosity smaller than of 1/3 core, and the aggregate, and phase 2 corresponds to the ITZ defined
which can be interpreted as a percolation threshold for diffusion between two concentric spheres of radius 𝑟1 and 𝑟2 . The spherical
in the fluid phase. In contrast with the MT scheme, the morphol- coordinates (𝑟, 𝜃, 𝜑) have their origins at the common centre of the
ogy of SC estimate consists in assuming that each particle (pore or spheres defined above, with axial symmetry around the 𝑥3 axis(see
solid) is embedded in the equivalent homogeneous medium. The Fig. 1).
SC scheme appears as the sole scheme able to consider percolation Each phase is defined by its volume fraction 𝑓𝑖 and by its diffusion
during the desaturation/resaturation mechanism of porous media. coefficient 𝐷𝑖 and respects both the Fick’s law. 𝐻 0 is considered to be
This conclusion is observed also for the elastic properties. How- parallel to the unit vector 𝑒3 : 𝐻 0 = 𝐻0 𝑒3 .
ever, it is interesting to note that in micro-mechanics, the porosity Solving the ionic diffusion equation with imposed condition 𝑐|∞ =
can be considered as a set of local inclusions surrounded by a 𝐻0 ⋅ 𝑥3 leads to:
cement matrix. In contrary, in diffusion, the solid material is ( )
𝑏
considered as inclusions embedded in a diffusive porous network. 𝑐𝑘 = 𝑎𝑘 𝑟 + 𝑘 𝑐𝑜𝑠𝜃 (8)
𝑟 2
• By comparing the terms involved in the equations linking defor-
mation and stress on the one hand and flow and concentration In this equation, 𝑎𝑘 and 𝑏𝑘 are constants. Two constants are already
on the other, it is possible to draw a parallel between Hooke’s known: 𝑏1 = 0 to avoid the singularity at the origin and 𝑎3 = 𝐻0 . The
law in micro-mechanics and Fick’s law for diffusion. The classical components of the flux vector of ions in the 3 dimensional problem
homogenization schemes, Mori–Tanaka and self-consistent esti- from the local Fick law equation give:
mates developed here and in the paragraphs 4.1 and 4.2, based ( )
𝑏
on the Eshelby theory and performed originally for mechanical 𝑗𝑘,𝑟 = −𝐷𝑘 𝑎𝑘 − 2 𝑘 𝑐𝑜𝑠𝜃 (9)
𝑟 3
problems can be also used to determine the effective diffusive ( )
𝑏
properties. Nevertheless, mechanics and diffusion are very phys- 𝑗𝑘,𝜃 = 𝐷𝑖 𝑎𝑘 + 𝑘 𝑠𝑖𝑛𝜃 (10)
𝑟3
ically different processes and requires their own analysis and
careful consideration as developed in the following. 𝑗𝑘,𝜑 = 0 (11)

The concentration gradient of each phase is thus linked with the

3. Interface consideration: n-layered inclusion problem
condition 𝐻0 at infinity and the tensor A𝑘 by the relation:
⟨ ⟩
Regarding the interface and the estimation of the localization tensor 1
𝑔𝑟𝑎𝑑 𝑐 𝑘 = 𝑔𝑟𝑎𝑑 𝑐 𝑘 𝑑𝛺 = A𝑘 ⋅ 𝐻0 = 𝐴𝑘 𝐻0 (12)
for an n-sphere composite, in 1993, Hervé and Zaoui [30] presented the 𝛺𝑘 𝛺𝑘 ∫𝛺𝑘
first n-layered inclusion model for predicting mechanical properties. It Considering that 𝐻0 = 𝐻0 𝑒3 , the third component of the average of
has subsequently been adapted for diffusion in [25,32]. Note that the the volume fraction of ions in each phase 𝛺𝑘 limited by 𝑆𝑘−1 and 𝑆𝑘 is
resolution method that is valid for a single type of inclusion can be determined by:
suitably applied to mortar including natural sand as a non-diffusive [ ]
⟨ ⟩
phase. It appears that, in the case of mortars containing several types 𝑘 1 𝑘 1
𝑐,3 = 𝑐,3 𝑑𝛺 = 𝑐𝑘 𝑛3 𝑑𝑆 − 𝑐𝑘 𝑛3 𝑑𝑆 = 𝑎𝑘 (13)
of aggregates, the direct application of this method is not appropriate. 𝛺𝑘 𝛺𝑘 ∫𝛺𝑘 𝛺𝑘 ∫𝑆𝑘 ∫𝑆𝑘−1
Dormieux and Lemarchand [33–35] determined localization tensors
where 𝑛3 (𝑛3 = 𝑐𝑜𝑠𝜃) denotes the third component of the unit outward
and homogenized diffusion coefficients for simple RVEs with central
normal to 𝑆𝑘−1 or to 𝑆𝑘 in a Cartesian coordinate system.
inclusion. The authors compare different homogenization schemes:
From Eq. (8), it can be deduced that (14):
the diluted, self-consistent, Mori–Tanaka, and differential schemes. ⟨ ⟩
An extension is given by Yang [36] for more complex RVEs with 𝑘
𝑐,3 = 𝑎𝑘 (14)
aggregates, and pores filled with water, pores filled with air. The two 𝛺𝑘

homogenization schemes proposed are the MT scheme and SC ones. The concentration coefficients of each phase can thus be calculated
Compared with the previous studies, the following developments from the parameters 𝑎𝑘 of each phase as presented in Annex:
will be added here, with mortars using different types of aggregates 𝑎𝑘
as explained below. 𝐴𝑘 = (15)
𝐻0

3
A. Abou-Chakra et al. Materials Today Communications 35 (2023) 105750

Fig. 2. 2D idealization of RVE for recycled cementitious composite: two homogenization schemes considered.

Fig. 3. Morphological representation of the mortar for the MT estimation.

In this study, the MT scheme is used and a fictitious uniform concen- 4.1. The Mori–Tanaka estimation
tration gradient, named 𝐻, is applied on the boundary of the RVE by:

⟨ ⟩ At the scale of the mortar, the RVE is illustrated in Fig. 3. It is

𝑔𝑟𝑎𝑑𝑐 =𝐻 (16) based on the representation of the n-layer spherical inclusions model
𝛺
The homogenized diffusion coefficient is then obtained (see Eq. (5)): defined by Hervé and Zaoui [30] considering the 𝑛 + 1 phases, where
( )−1 the cement matrix (c) is not the equivalent homogeneous medium.
∑ ∑ 𝑎 The representation of the mortar is thus defined by a sum of two 2-
𝐷ℎ𝑜𝑚 = 𝜙𝑘 𝐷𝑘 𝐴𝑘 𝐴𝑘 with 𝐴𝑘 = 𝑘 (17)
𝑘 𝑘
𝐻 0 layer spherical inclusions: the sand (s) and rubber aggregates (ra), and
When the self-consistent scheme is adopted to estimate the homoge- the interfacial transition zones (s-c) and (ra-c) embedded in a cement
nized diffusion coefficient, there is no matrix as a phase. All inclusions matrix (c).
are embedded in the equivalent homogeneous medium, 𝐷ℎ𝑜𝑚 . From Annex for spherical inclusions with 2 shells is applied twice with:
Annex, it can be seen that, for an n-layered model, the coefficients
⎧ 𝐷 = 𝐷𝑠 = 0 ∀𝑧 ∈ 𝛺𝑠
𝑎𝑘 depend on the diffusion coefficient of the infinite medium, 𝐷ℎ𝑜𝑚 ⎪ 1
in the case of the self-consistent scheme. Eq. (17) becomes an implicit ⎨ 𝐷2 = 𝐷𝑠−𝑐 ∀𝑧 ∈ 𝛺𝑠−𝑐 (18)
equation in 𝐷ℎ𝑜𝑚 . ⎪ 𝐷3 = 𝐷𝑐 ∀𝑧 ∈ 𝛺𝑐
⎩

4. Prediction of diffusion properties of mortars incorporating un- and

conventional aggregates ⎧ 𝐷 = 𝐷𝑟𝑎 ∀𝑧 ∈ 𝛺𝑟𝑎
⎪ 1
⎨ 𝐷2 = 𝐷𝑟𝑎−𝑐 ∀𝑧 ∈ 𝛺𝑟𝑎−𝑐 (19)
The aim of this section is to apply the model detailed previously
⎪ 𝐷3 = 𝐷𝑐 ∀𝑧 ∈ 𝛺𝑐
to predict diffusion properties of mortars taking the properties of ⎩
the aggregates used into account. The phases considered are: cement
where 𝐷𝑖 denotes the diffusive coefficient of the phase (𝑖).
paste, sand, rubber aggregates, and ITZs. The macroscopic diffusion is
estimated by the MT and SC schemes. Localization coefficients obtained are listed below:
In Fig. 2, are represented two RVEs for recycled cementitious ⎧ 𝑓𝑟𝑎 + 𝑓𝑟𝑎−𝑐
9
composite corresponding to the two estimates, MT and SC ones. The ⎪ 𝐴𝑟𝑎 =
2 𝐷𝑟𝑎 𝐷 𝐷 3 1
Fig. 2(a) represents the RVE for the MT estimate where a random ⎪ 3𝑓𝑟𝑎 + 2𝑓𝑟𝑎−𝑐 + 𝑓 + 𝑟𝑎−𝑐 𝑓𝑟𝑎−𝑐 + 𝑟𝑎 ( 𝑓𝑟𝑎 + 𝑓𝑟𝑎−𝑐 )
⎪ 𝐷𝑟𝑎−𝑐 𝑟𝑎−𝑐 𝐷𝑐 𝐷𝑐 2 2
distribution of families of spherical inclusions, sand and rubber ag- ⎪
⎪ 𝐴𝑟𝑎−𝑐 2 1 𝐷𝑟𝑎
gregates, and their corresponding ITZ is embedded in the cement =( + )𝐴
⎪ 3 3 𝐷𝑟𝑎−𝑐 𝑟𝑎
paste. In contrast, the SC scheme was originally developed for granular ⎨
⎪𝐴 9 (𝑓𝑠 + 𝑓𝑠−𝑐 )𝐷𝑐
microstructure and assumes no matrix phase, and all the phases even in =
⎪ 𝑠 2 3𝑓𝑠 𝐷𝑐 + 2𝑓𝑠−𝑐 𝐷𝑐 + 𝐷𝑠−𝑐 𝑓𝑠−𝑐
our case the cement paste play a symmetric role. A similar reasoning as ⎪
the MT estimate can be considered with, as Fig. 2(b), all the aggregates ⎪ 𝐴𝑠−𝑐 2
= 𝐴𝑠
and even the cement paste are seen as inclusions embedded in the ⎪ 3
⎪𝐴 =1
reference medium. The medium considered at the mortar scale is ⎩ 𝑐
then a set of concentric spheres placed inside a homogeneous matrix (20)
having the properties of the mortar. At this scale, all phases, including
aggregates, may be diffusive. where 𝑓𝑖 denotes the volume fraction of the phase (𝑖).

4
A. Abou-Chakra et al. Materials Today Communications 35 (2023) 105750

Fig. 4. Morphological representation of the mortar for the SC estimation.

Table 1
Control and rubberized mortar mixes.
Formulations REF RA5 RA15 RA30
Substitution rate (%) 0 5 15 30
Cement CEM III/C 32,5 N PM/ES (kg m3 ) 242 224 228 225
Water (kg m3 ) 254 235 239 236
Semi-crushed sand 0/4 (kg m3 ) 1644 1546 1318 1071
Filler (kg m3 ) 135 135 135 135
Rubber aggregates (kg m3 ) 0 34 104 206
Super-plasticizer (kg m3 ) 4.7 7.2 7.2 7.2
Viscosity agent (kg m3 ) 0 1.1 1.1 1.1

The diffusion coefficient homogenized by MT estimation may be Table 2

Porosity for rubberized mortars.
expressed as:
Substitution ratio (%) Porosity (%)
𝑓𝑐 𝐴𝑐 𝐷𝑐 + 𝑓𝑠−𝑐 𝐴𝑠−𝑐 𝐷𝑠−𝑐 + 𝑓𝑟𝑎 𝐴𝑟𝑎 𝐷𝑟𝑎 + 𝑓𝑟𝑎−𝑐 𝐴𝑟𝑎−𝑐 𝐷𝑟𝑎−𝑐
𝐷ℎ𝑜𝑚 = (21) 0 19.0
𝑓𝑐 𝐴𝑐 + 𝑓𝑠 𝐴𝑠 + 𝑓𝑠−𝑐 𝐴𝑠−𝑐 + 𝑓𝑟𝑎 𝐴𝑟𝑎 + 𝑓𝑟𝑎−𝑐 𝐴𝑟𝑎−𝑐 5 20.0
15 22.5
4.2. The self-consistent estimation 30 31.5

As for the MT estimation, the SC scheme is applied for the es-

timation of the macroscopic diffusion coefficient. All phases, even
the same volume of rubber aggregates. The influence of the rate of
the cement paste, are now considered as spherical inclusions as illus-
substitution of sand by rubber aggregates is the main parameter studied
trated in Fig. 4. The RVE is now a 4-layer spherical representation
in this part. A mix using natural sand and CEM III/C 32,5N PM/E
of inclusions: cement paste (c), inclusions (s), ITZs (s-c) and (ra-c)
cement was considered as the control mortar (REF mix in Table 1).
in a Homogenous Effective Medium (HEM), which is the sum of all
The volume fraction of the sand was 62%. In this study, CEM III/C
inclusions:
was chosen instead of CEM I because of its better sustainability in
The localization coefficients obtained are listed below:
aggressive environment (XA1 to XA3 exposition class in NF EN 206/CN
⎧ 9 𝑓𝑟𝑎 + 𝑓𝑟𝑎−𝑐 in accordance with Eurocode NF EN 1992-1-1) and its lower sensitivity
⎪ 𝐴𝑟𝑎 = to external sulphate attack in targeted applications where transfer
⎪ 2 𝐷𝑟𝑎 𝐷 𝐷 3 1
⎪ 3𝑓𝑟𝑎 + 2𝑓𝑟𝑎−𝑐 + 𝑓 + 𝑟𝑎−𝑐 𝑓 + 𝑟𝑎 ( 𝑓 + 𝑓 ) properties of the cement-based composite play a prominent role.
𝐷𝑟𝑎−𝑐 𝑟𝑎−𝑐 𝐷ℎ𝑜𝑚 𝑟𝑎−𝑐 𝐷ℎ𝑜𝑚 2 𝑟𝑎 2 𝑟𝑎−𝑐
⎪ Rubberized mortars were obtained from the control mix by replac-
⎪ 2 1 𝐷𝑟𝑎
⎪ 𝐴𝑟𝑎−𝑐 =( + )𝐴 ing a volume of natural sand by rubber aggregates. The volume fraction
3 3 𝐷𝑟𝑎−𝑐 𝑟𝑎
⎪ of cement paste was maintained constant. Different replacement rates
⎨ 9 (𝑓𝑠 + 𝑓𝑠−𝑐 )𝐷ℎ𝑜𝑚
⎪ 𝐴𝑠 = of sand by rubber aggregates were tested: RA5, RA15 and RA30 stand-
⎪ 2 3𝑓𝑠 𝐷ℎ𝑜𝑚 + 2𝑓𝑠−𝑐 𝐷ℎ𝑜𝑚 + 𝐷𝑠−𝑐 𝑓𝑠−𝑐
ing for 5, 15 and 30% respectively (Table 1). Based on the grain size
⎪ 2
⎪ 𝐴𝑠−𝑐 = 𝐴𝑠 distribution, the sand average diameter is same order as the rubber
3
⎪ aggregates, estimated to be 750 μm and 650 μm, respectively.
⎪𝐴 3 𝐷ℎ𝑜𝑚
=
⎪ 𝑐 2 𝐷ℎ𝑜𝑚 + 𝐷𝑐
⎩
5.1. Porous media
(22)

As previously, the effective diffusion coefficient is deduced from
Eqs. (17) and (22).
5. Input data model
Various cementitious mortars using different types of aggregates, in-
cluding natural sand and rubber aggregates, with different volume frac-
tions were investigated. For each mortar, the use of the water/cement
(w/c) ratio was maintained to avoid the segregation constant. Admix-
tures (superplasticizer and in the case where rubber aggregates were
used, viscosity agent) were adjusted in order to maintain the slump
between 18 and 22 cm; their effects on the diffusion properties of
the cement paste were considered as negligible. Rubberized mortars
were obtained by replacing a part of the volume of natural sand by
Most of the aggressive phenomena that can affect these cemen-
titious materials are linked to the diffusion of an aggressive agent
into their porous media. Therefore, it is essential to characterize the
physical properties of the mortars that are in direct relation with the
diffusion phenomenon, such as water porosity. Experimental character-
ization was conducted in accordance with AFGC AFREM recommenda-
tions [37] and results are presented in Table 2.
Considering that rubber aggregates are not porous, the increase of
the porosity accessible to water must be directly due to entrapped air
bubbles particularly supported by the hydrophobic behaviour of the
rubber aggregates present. Then, the increase of porosity for rubberized
mortar results is a consequence of a more porous cement paste and of
bond defects between matrix and rubber aggregates resulting in a wider
ITZ [38]. The mortar with 30% of sand replaced by rubber aggregates

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A. Abou-Chakra et al. Materials Today Communications 35 (2023) 105750

Table 3
Volume fractions of different phases and for different formulations.
Formulations REF RA5 RA15 RA30
𝑓𝑠 0.616 0.542 0.494 0.401
𝑓𝑟𝑎 0 0.028 0.087 0.172

has a very high porosity of 31% (ie +12% relative to the reference
mortar) which can significantly affect its transfer properties.

5.2. Aggregate volume ratio

The REF mortar contained 1644 kg(ms) of sand for one m3 of mortar.
From specification data, the sand relative density was equal to 2.67.
The volume ratio of sand was then obtained by using: Fig. 5. Rubber aggregate in cement paste.
𝑚𝑠 1644 Source: From [45].
𝑓𝑠 = = = 0.616 (23)
𝑉 𝑚 𝜌𝑠 1 ⋅ 2670
The density of 𝑅𝐴 = 1.2. (See Table 3.)

5.3. Interfacial transition zones

(a) Sand ITZ

The ITZ between sand aggregates and cement paste is considered
in the proposed model. It is well known that this zone is the
weakest part of the cementitious composite. It is characterized
by a greater capillary porosity than the matrix. Its thickness
and properties depend on many parameters, such as the type of
aggregates or cement, the proportion of mineral additions or the
W/C ratio.
The ITZ volume fraction was determined from the average aggre-
gates radius 𝑟𝑠 and its thickness 𝑒𝑠−𝑐 using the expression below:
(𝑟𝑠 + 𝑒𝑠−𝑐 )3 − 𝑟3𝑠
𝑓𝑠−𝑐 = 𝑓𝑠
𝑟3𝑠
It should be noted that a wide range of studies have been done
on the ITZ topic, leading to a wide spectrum of results, which
may even be contradictory, especially as far as its thickness
is concerned. Some authors estimated a relatively small ITZ
thickness, below 20 μm [39,40]. Others observed that the ITZ
thickness varies between 50 and 100 μm [41].
To characterize the ITZ in the rest of the study, some obser-
vations were made using both Scanning Electron Microscopy
observations and X-ray micro-tomography. It should be men-
tioned that thicknesses less than 25 μm (voxel size: 11 μm)
cannot be observed on X-ray images. From the images obtained,
no interface was seen which indicates that the ITZ thickness was
less than 25 μm. SEM observations confirmed this first finding
and indicated a thickness of around 10 μm [42]. In the following,
a thickness of 10 μm is thus assumed. As described in the input
data section, the sand average diameter is estimated to be 750
μm (ie 𝑟𝑠 = 375 μm). The ITZ volume fraction of the REF mortar
is then deduced from the following equation:
(375 + 10)3 − 3753
𝑓𝑠−𝑐 = 𝑓𝑠
3753
(b) Rubber aggregates ITZ
The hydrophobic nature of the rubber aggregates leads to a wide,
porous ITZ between the rubber surface and cement paste as
observed in [43,44] and illustrated in Fig. 5 from [45]. X-ray
micro-tomography observations from Fig. 6 show a weak adher-
ence between rubber aggregates and cement paste. It is worth
noticing that the observation from Fig. 5 is very different from
the one on cement based materials containing recycled concrete
aggregates (see for example [1,46]). Indeed, [47] observed two
ITZs, one between aggregate and new paste but also another one
between old paste and aggregate.
Fig. 6. ITZ Observation of rubber aggregates from X-ray microtomography.
(24)
Regarding the materials containing rubber aggregates, a previ-
ous study [45] estimated the ITZ thickness, highlighted in red
in Fig. 5, at approximately 30 μm. Our current observation from
the X-ray micro-tomography image (Fig. 6) gives a thickness
of 50 μm. The calibration of the model parameters with the
experimental data from the REF mortar leads to an ITZ thickness
of 50 μm for the MT estimate and 30 μm for SC one (see Table 4).
The ITZ volume fraction is deduced from Eq. (25) for an average
radii of rubber aggregate around 650 μm.
5.4. Diffusion coefficients
(a) Diffusion coefficient of aggregates
The porosity of the sand and that of rubber aggregates is negligi-
ble. These phases will therefore be considered as non-diffusive.
(b) Diffusion coefficients
The diffusion coefficient of the cement paste and those of ITZs
are obtained by fitting with experimental data from REF mortar,
as indicated in Tables 5 and 6 for the MT and SC schemes
(25) respectively. The fitting values obtained by the MT scheme show
a significant difference, (15 times), between the diffusion of
the cement paste and the sand aggregates ITZ (Table 5). The
difference can be explained by the high porosity inside the
ITZ compared with the cement paste. On the other hand, the
diffusion values obtained by fitting with the SC model of the
paste and the ITZ are similar ( Table 6). Consequently, the high
volume of pores inside the ITZ is only considered by the MT
model, which seems to be the best estimation scheme to describe
the ITZ influence when sand is used as an aggregate. Regarding
the rubber aggregates, they are assumed to be non-diffusive as
the natural sand aggregates.

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A. Abou-Chakra et al. Materials Today Communications 35 (2023) 105750

Table 4
Volume ratio of rubber aggregates.
REF RA5 RA15 RA30
Volume ratio of sand 𝑓𝑠 0.616 0.542 0.494 0.401
ITZ thickness 𝑒𝑠−𝑐 (μm) 10
Sand Volume ratio of ITZ 𝑓𝑠−𝑐 0.051 0.045 0.040 0.033
Volume ratio 𝑓𝑟𝑎 0 0.0283 0.0867 0.172
Rubber aggregates ITZ thickness 𝑒𝑟𝑎−𝑐 (μm) 50
(Parameters MT) Volume ratio of ITZ 𝑓𝑟𝑎−𝑐 0 0.01 0.031 0.061
Rubber aggregates ITZ thickness 𝑒𝑟𝑎−𝑐 (μm) 30
(Parameters SC) Volume ratio of ITZ 𝑓𝑟𝑎−𝑐 0 0.0041 0.012 0.025

Table 5 Table 7
Diffusion values (m2 ∕s) from fitting and bibliography for the MT scheme (Parameters Diffusion values (m2 ∕s) from fitting and bibliography for the SC and MT schemes.
MT). Diffusion coefficient REF RA5 RA15 RA30
Diffusion coefficient REF RA5 RA15 RA30
𝐷𝑒𝑥𝑝 1.89 × 10−12 2.36 × 10−12 2.64 × 10−12 3.29 × 10−12
𝐷𝑐 2.2 × 10−12 𝐷ℎ𝑜𝑚 MT 1.87 × 10−12 2.12 × 10−12 2.63 × 10−12 3.53 × 10−12
𝐷𝑠 0 Rel. error (%) 1.2 10.3 0.46 7.4
𝐷𝑠−𝑐 ∕𝐷𝑐 15 𝐷ℎ𝑜𝑚 SC 1.87 × 10−12 2.55 × 10−12 2.84 × 10−12 3.56 × 10−12
𝐷𝑟𝑎 0 Rel. error (%) 1.05 8.05 7.56 8.21
𝐷𝑟𝑎−𝑐 1 × 10−9

Table 6
Diffusion values (m2 ∕s) from fitting and literature for the self-consistent scheme (SC
parameters).
Diffusion coefficient REF RA5 RA15
𝐷𝑐 1.15 × 10−11
𝐷𝑠 0
𝐷𝑠−𝑐 1 × 10−11
𝐷𝑟𝑎 0 electrical potential is then applied in accordance the NT BUILD 492
𝐷𝑟𝑎−𝑐 5 × 10−11
6. Sensitivity study on parameters and predictions
6.1. Parameters sensitivity: influence of the ITZ and diffusion values
In order to evaluate the sensitivity of the predicted results to the
ITZ thickness, the evolution of the normalized diffusion coefficient
from the MT scheme with the ITZ thickness of sand for the reference
mortar is presented in Fig. 7(a) (The normalized coefficient is the
ratio of the homogenized diffusion coefficient, 𝐷ℎ𝑜𝑚 , and the reference
diffusion coefficient measured on the reference mortar REF 𝐷𝑅𝐸𝐹 ). The
modelling result shows that the predicted diffusion is sensitive to the
ITZ thickness increasing by 3 orders for 𝑒 = 50 μm. The evolution
of the diffusion coefficient for mortar containing rubber aggregates is
presented in Fig. 7(b). It is also sensitive to the ITZ thickness for rubber
aggregates but with a steeper curve than the reference mortar one.
The influence of the parameter 𝐷𝑠−𝑐 can also be evaluated from
the curve linking the ratio 𝐷ℎ𝑜𝑚 ∕𝐷𝑒𝑥𝑝 versus the ratio 𝐷𝑠−𝑐 ∕𝐷𝑐 for
the reference mortar RA30 and the MT scheme (see Fig. 8). It can be
observed that the value of 𝐷𝑠−𝑐 impacts the macroscopic behaviour
significantly. Based on Fig. 7(b) and Fig. 8, the ITZ thickness and its
transfer properties both have an important effect on the macroscopic
predictions.
The same conclusion can be drawn with the SC scheme; see Figs. 9(a)
and 9(b). The SC and MT estimates are both sensitive to the parameters
ITZ thickness 𝑒𝑟𝑎−𝑐 and ITZ diffusion coefficient 𝐷𝑟𝑎−𝑐 . Compared to the
MT predictions for an RA30 mortar and a thickness of 40 μm, the ratio
𝐷ℎ𝑜𝑚 ∕𝐷𝑅𝐸𝐹 from the SC scheme is higher but remains comparable.
6.2. Calibration and validation
The predicted values of the mortar diffusion coefficient obtained by
the MT and SC schemes were compared with the experimental data
(see Table 7) with a wide range of rubber volume fractions between
0% and 30%. The experimental diffusion coefficients were obtained
from chloride ion diffusion tests in accordance with the NT BUILD 492
standard [48], an electrical method similar to the rapid chloride (RCP)
RA30
test. This test is conducted on cylindrical mortar specimens having a
diameter of 118 mm and a height 50 mm. The sample is sandwiched
between a sodium hydroxide solution at 0.3 mol/L (anolyte) at the top
and a 2 mol/L sodium chloride solution (catholyte) at the bottom. An
standard. The diffusion coefficient (or in the standard Non-Steady State
Chloride Migration) is obtained from values of chloride depth pene-
tration, exposure time, sample thickness, voltage and average sample
temperature. The results obtained for the different mortars are reported
in Table 7. The comparison shows a low relative error, under 10%, for
both SC and MT estimates. Both predictions are accurate to predict the
diffusion coefficient of mortar incorporating rubber aggregates. From
Fig. 8, it can be noted that the diffusion through the material increased
with the volume fraction of rubber aggregate. It also appears that the
effect of aggregate types on the transfer properties depends more on
the induced ITZ than on their own properties. When rubber aggregates
were used, the ITZ had a prominent effect on the material properties
due to its greater thickness and higher porosity (see Table 2). In the
following section, a parametric study is conducted in which several
model parameters are varied to better understand the influence of each
micro parameter on the macro diffusion.
6.3. Validation on another mix design
To validate the previous estimates to other mix designs and in the
context of light-weight mortars (called also low-strength mortars [31]),
cementitious composites containing different ratio of expanded clay
aggregates are investigated in this paragraph. Compared with normal-
strength or high-strength concrete properties, the diffusive properties
of this type of mortars is completely unknown. The purpose of this
section is not only to validate the extended SC and MT schemes to other
mix designs but also to give formulas of diffusion coefficient for a wide
range of materials depending on the composition data.
The cementitious composite mix investigated here is composed of
sand, expanded clay and cement paste. Different substitution rates
are tested: EC30 and EC60 standing for 30% and 60%, respectively
(Table 8). The aggregates were pre-saturated before mixing according
to their data-sheet.
The ITZ of sand is considered with the same thickness value as
in the study of mortars containing rubber aggregates. From Scanning
Electron Microscopy observations, the ITZ of expanded clay aggregates
was identified as non-existent, as shown in Fig. 11. According to [49],

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A. Abou-Chakra et al. Materials Today Communications 35 (2023) 105750

Fig. 7. Evolution of the ratio 𝐷ℎ𝑜𝑚 ∕𝐷𝑅𝐸𝐹 of the reference mortar REF Fig. 7(a) and the mortar with rubber aggregates RA30 Fig. 7(b) for the MT scheme with the ITZ thickness.

The predicted diffusion coefficient is compared with experimental

data in Table 10 for the mix designs EC30 and EC60 corresponding
to substitution rates of sand of 30% and 60%. The input data for the
sand aggregates and the cement paste are kept identical to the previous
section dedicated on rubber aggregates mortars. From Table 10, it
appears clearly that the results are very satisfactory for both schemes
with still a smaller relative error for the SC scheme compare to the MT
one.

7. Conclusion

Two different multi-scale approaches for the prediction of diffusion

properties of cementitious materials have been presented in this paper.
The aim was to estimate the diffusion properties of different mor-
tars with several types of aggregates (natural sand, rubber aggregate,
extended clay aggregate). For these materials, the diffusion of ionic
Fig. 8. Evolution of the ratio 𝐷ℎ𝑜𝑚 ∕𝐷𝑅𝐸𝐹 for the MT scheme with the ratio 𝐷𝑠−𝑐 ∕𝐷𝑐 . species takes place not only through the porous network of the cement
matrix but also at the ITZ between sand and cement paste or between
Table 8 rubber aggregates and cement paste. Classical homogenization schemes
Expanded clay mortar mixes. (dilute, Mori–Tanaka and self-consistent schemes) do not allow the
Substitution rate (%) 0 30 60 ITZ around the aggregates to be taken into account directly and tend
Cement CEM III/C 32,5 N PM/ES (kg m3 ) 242 242 242 to underestimate the diffusion properties. The model developed in
Water (kg m3 ) 254 254 254 this study was based on a spherical n-phase inclusion model first
Semi-crushed sand 0/4 (kg m3 ) 1644 1151 658
introduced for a multi-shell morphology surrounding one type of core
Filler (kg m3 ) 135 135 135
Pre-saturated expanded clay aggregates (kg m3 ) 0 241 482
and embedded in the equivalent homogeneous medium (EHM), the SC
Super-plasticizer (kg m3 ) 4.7 4.7 4.7 estimate. The spherical n-phase inclusion model was then extended to
Viscosity agent (kg m3 ) 0 1.2 1.2 a multi-reinforced composite composed of different types of aggregates
surrounded by their specific ITZ and embedded in a cement matrix. The
MT scheme was used considering a matrix with the property of the ce-
ment paste and not anymore seen as the EHM. The two homogenization
the high porosity of the external shell of those aggregates allows the
schemes, MT and SC, were then compared with experimental data and
cement paste to penetrate their surface and guarantees the hypothesis
some conclusions can be made:
of the continuity for displacements and stress fields. In the present case,
X-ray microtomography analyses did not show an interface between the • MT’s approach seems to be the most satisfactory and the param-
matrix and the clay aggregates (Fig. 11). Finer observations at SEM eters calibrated are closer to reality.
showed a thickness between 0 and 5 μm depending on the location • Whereas a RVE is quite different between the two schemes, the
(Fig. 10). In order to simplify the model, we will consider here that results are both in accordance with experimental results.
the interface is negligible (see Fig. 11). • The replacement of natural aggregates (sand) by rubber aggre-
The composition and the data used are summarized in Table 9. The gates increases the diffusion properties of the material mainly
diffusion coefficient of expanded clay aggregates is obtained by fitting because of a wider and more porous ITZ. The influence of the
with experimental data from REF mortar as in Section 5.4. The diffusion different parameters on the diffusion properties has been studied
coefficient obtained for the MT and SC scheme are 3.50 × 10−12 and in order to understand the link between the microstructure and
3.00 × 10−12 m2 ∕s, respectively. the effective diffusion properties.

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A. Abou-Chakra et al. Materials Today Communications 35 (2023) 105750

Fig. 9. Parametric study of the self-consistent scheme.

Table 9
Input data for the mortar containing expanded clay aggregates.
REF EC30 EC60
Volume ratio of sand 𝑓𝑠 0.616 0.431 0.246
Sand ITZ thickness 𝑒𝑠−𝑐 (μm) 10
𝐷𝑠−𝑐 (m2 ∕s) 1.00 × 10−12
Expanded clay Volume ratio 𝑓𝑒𝑐 0 0.183 0.366
Expanded clay (Parameters MT) 𝐷𝑒𝑐 (m2 ∕s) 3.50 × 10−12
Expanded clay (Parameters SC) 𝐷𝑒𝑐 (m2 ∕s) 3.00 × 10−12

9
A. Abou-Chakra et al. Materials Today Communications 35 (2023) 105750

Fig. 10. ITZ observation of expanded clay aggregates from MEB.

Fig. 11. ITZ observation of expanded clay aggregates from X-ray microtomography.

Table 10 CRediT authorship contribution statement

Diffusion values (m2 ∕s) for the SC and MT schemes.
Diffusion coefficient REF EC30 EC60
A. Abou-Chakra: Writing – original draft, Methodology, Concep-
𝐷𝑒𝑥𝑝 1.89 × 10−12 2.88 × 10−12 3.98 × 10−12
tualization, Validation, Verification. G. Blanc: Performing the exper-
𝐷ℎ𝑜𝑚 MT 1.83 × 10−12 2.84 × 10−12 3.73 × 10−12
Rel. error (%) 3.17 1.39 6.28 iments, Data/evidence collection, Writing – original draft, Provision
𝐷ℎ𝑜𝑚 SC 1.87 × 10−12 2.88 × 10−12 3.98 × 10−12 of study materials, Laboratory samples. A. Turatsinze: Supervision,
Rel. error (%) 1.06 4.17 0.00 Writing - reviewing. G. Escadeillas: Supervision, Writing - reviewing.

Declaration of competing interest

• It appears from the MT predictions that the ITZ has a significant
effect on the macroscopic properties. These models have also been The authors declare that they have no known competing finan-
extended to mortars containing other types of aggregates and cial interests or personal relationships that could have appeared to
validated by comparison with experimental data. The conclusion influence the work reported in this paper.
goes in the same way as the one on mortar containing rubber
aggregates, the MT and SC schemes seem efficient to predict the
Data availability
properties of low-strength mortars.

No data was used for the research described in the article.

Based on this conclusion, an interesting direction could be explored:
consider at the cement-paste scale the SC scheme which can consider
the percolation during the desaturation/resaturation mechanism of Acknowledgements
porous media and the MT scheme at the scale of mortar which is closer
to the morphology of reinforced-composite composed of a surrounded We would like to thank the Menard company, France for its financial
cement paste phase. support and the great interest it showed in our work.

10
A. Abou-Chakra et al. Materials Today Communications 35 (2023) 105750

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[7] RILEM State Art Reports, in: H. Beushausen, L. Fernandez Luco (Eds.),
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