Construction and Building Materials 254 (2020) 119042

Contents lists available at ScienceDirect

Construction and Building Materials

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

Assessment of packing, flowability, hydration kinetics, and strength of

blended cements with illitic calcined shale
Guillermina Marchetti a,⇑, Viviana Rahhal a, Zbyšek Pavlík b, Milena Pavlíková b, Edgardo F. Irassar a
a
Departamento de Ingeniería Civil, Facultad de Ingeniería, Universidad Nacional del Centro de la Provincia de Buenos Aires, Av. del Valle 5737, B7400JWI Olavarría, Argentina
b
Department of Materials Engineering and Chemistry, Faculty of Civil Engineering, Czech Technical University in Prague, Thákurova 7, 166 29 Prague 6, Czech Republic

h i g h l i g h t s

Illitic calcined shale have great potential as low-energy and low-carbon SCM.

The packing density of blended cement paste decreases, but it increases for mortar.

The flowability depends on the particle size distribution and the specific surface area.

Blended cements with illitic calcined shale show the CH-reduction and the pore size refinement.

The compressive strength of blended cements is higher than the OPC mortar 90 days.

a r t i c l e i n f o a b s t r a c t

Article history: The effects of two illitic calcined shales as supplementary cementitious materials (SCMs) on the perfor-
Received 12 December 2019 mance of ordinary Portland cement (OPC)-based pastes and mortars were investigated. The packing den-
Received in revised form 19 March 2020 sity of blended cement pastes and mortars were predicted with compressible packing model (CPM). The
Accepted 5 April 2020
water film thickness (WFT) and flowability were calculated and measured. Early hydration was described
by calorimetric curves and the hydration microstructure was identified by X-ray diffraction (XRD), differ-
ential thermal analysis (DSC/TG), and pore size distribution (MIP). The compressive strength was tested
Keywords:
at 2, 7, 28, and 90 days. The results showed that the partial replacement of OPC by illitic calcined shale
Blended cement
Calcined clay
decreased the packing density and the flowability of cement pastes but this does not occur for standard
Illite mortars. For blended cements, the hydration products were similar to that corresponding to OPC, the
Packing pozzolanic reaction contributed from 28 days to the densifying of solid structure and it was also noticed
Flowability the pore size refinement that improved the compressive strength at later age.
Hydration Ó 2020 Elsevier Ltd. All rights reserved.
Strength

1. Introduction the calcinations temperature, it is also possible to improve the

Concrete is the building material with the greatest potential to
meet the growing housing demand in developing countries, and
Portland cement is its high embodied energy and CO2-emmision
component. However, locally available materials should be consid-
ered as a possible replacement, to reduce the costs and environ-
mental impact associated with cement production. The
utilization of calcined clay or calcined shale as a pozzolanic addi-
tion for mortar and concrete is widely recommended to reduce
CO2 emission due to their great availability and enhancement of
durability. Additionally, depending on clay mineral present and
⇑ Corresponding author.
E-mail addresses: gmarchetti@fio.unicen.edu.ar (G. Marchetti), vrahhal@fio.
unicen.edu.ar (V. Rahhal), pavlikz@fsv.cvut.cz (Z. Pavlík), milena.pavlikova@fsv.
cvut.cz (M. Pavlíková), firassar@fio.unicen.edu.ar (E.F. Irassar).
strength, due to a combination of the filler effect and the stimula-
tion of cement hydration. Several studies have demonstrated the
effectiveness of calcined clays, particularly for kaolinitic clay to
produce metakaolin with increased pozzolanity [1–3]. However,
there are other calcined clays barely used as supplementary
cementitious materials (SCMs) due to the complexity of clay min-
erals and lack of knowledge of the reaction mechanisms. Illitic
clays or shale have a high activation temperature and their poz-
zolanic activity is slow compared with kaolinitic clays, but it is
the most abundant type of clay in several regions of the world
and therefore their potential as SCM in cement based materials
contributing to reduce the environmental impact is high. Previous
studies [4,5] have shown that the addition of illitic calcined clays
as cement replacement has little effect on the water demand and
28-days strength, but could slow down the rate of strength devel-
opment at earlier age. For high replacement levels, this type of cal-

https://doi.org/10.1016/j.conbuildmat.2020.119042
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
2 G. Marchetti et al. / Construction and Building Materials 254 (2020) 119042

cined clays reduces the early compressive strength due to the dilu-
tion effect. He et al. [3] have studied illitic clays thermally activated
at three different temperatures (650, 750 and 930 °C) and have
demonstrated that the highest pozzolanic activity is produced with
the calcination at 930 °C, reaching to 79% of the compressive
strength of reference OPC after 28 days. Lemma et al. [4] have indi-
cated that illitic clays are appropriate as raw material to prepare
calcined pozzolan when fired at 950 °C. Garg et al. [6] have demon-
strated that illite-smectite clay exhibits the optimum reactivity
when fired at 900 °C, and the white Portland cement-calcined clay
blend (mass ratio 70/30) revealed a small degree of calcined clay
reaction at early age, but an important degree of reaction after pro-
longed hydration.
An important property of cementitious materials, that affects
the rheological and strength performance, is the packing density,
which determines the amount of voids between particles to be
filled with water. Essentially, when the packing density is high, less
water would be needed to fill the voids, and at the same water/
cementitious materials ratio (w/cm) more water in excess is
released to increase the flowability. In addition, at the same flowa-
bility requirement, it would allow to reduce the w/cm and thereby
increase the strength [7].
From several studies [8–11], it can be inferred that the most
important factors affecting the rheology of cement pastes/mortars
are the packing density, the water content, and the surface area of
the particles in the mixture. Kaufmann et al. [12] studied cement
pastes containing different SCMs (metakaolin, silica fume, ultrafine
cement or limestone filler) and found that blending the ordinary
cement with finer SCM can improve the rheological properties of
cement paste. Some researchers [13–15] developed a method for
measuring the packing density of granular materials. This method,
called wet packing method, is capable of simulating the wet condi-
tion in fresh cement paste/mortar and allowing the presence of any
type of superplasticizer (SP) which may have significant effect on
the packing density. The results obtained indicated that the com-
bined effects of packing density, water content and surface area
can be evaluated in terms of the water film thickness (WFT) of
the mixture and that the WFT is an important factor governing
the rheology of pastes and mortars [11,16–18,19]. Furthermore,
to predict the packing density of blended cement, the compressible
cement. Common clays, including illitic shales, are in the same
market niche and they have a great potential to become eco-
efficient, cheap, and sustainable alternative SCM [46].
2. Experimental
2.1. Materials
An Ordinary Portland Cement (OPC) supplied by Loma Negra
CIASA (Olavarría, Argentina) and two natural illitic shales (I1 and
I2) from L’amalí (Olavarría) and La Cabañita (San Jacinto) quarries
were used. They were calcined at 950 °C (MI1 and MI2) and ground
until the retained on 45 mm sieve was lower than 12%.The calcina-
tion temperature was chosen according to the original work pub-
lished by Lemma et al. [4]. The specific densities of these
powders measured according to ASTM C 188 [27] were 3.13 g/cm3
(OPC), 2.63 g/cm3 (MI1) and 2.72 g/cm3 (MI2). The corresponding
surface areas measured by Blaine test method (ASTM C 204 [28])
were 354, 622, and 507 m2/kg, respectively.
The chemical and mineralogical composition of cement and
both illitic calcined shale is reported in Table 1. The chemical com-
position was determined using an Axios sequential WD-XRF spec-
trometer (PANalytical, Almelo). The resulting data were collected
by SuperQ software, and further evaluated by Omnian software.
The mineralogical composition of both SCM was determined using
Rietveld method with external standard on X-ray diffraction (XRD)
patterns collected on Philips PW 3710 diffractometer (PANalytical,
Almelo) operating with CuKa radiation at 40 kV and 20 mA, using a
carbon monochromator.
For the fine aggregate (FA), CEN-standard sand (Normensand
GmbH, Germany) according to the EN 196-1 [29] was used. Its den-
sity was 2.65 g/cm3, and the calculated specific surface area was
8.1 m2/kg. The particle size distribution of OPC, MI1, MI2 and FA
was determined using a laser diffraction particle size analyzer
(Malvern Mastersize 2000) and the accumulated volume curve is
Table 1
Chemical and mineralogical composition of cementitious materials.

packing model (CPM) has good correlation with the experimental OPC MI1 MI2
values obtained with the wet packing method [15,20]. Chemical composition [wt.%]
The performance of blended cements containing calcined natu- SiO2 20.14 66.30 62.61
ral pozzolans depends on the evolution of hydration of the fraction Al2O3 4.20 16.28 18.28
of clinker and the pozzolan. The replacement of Portland cement Fe2O3 4.46 9.23 7.79
CaO 60.48 0.33 0.77
by SCM causes the dilution effect that can be computed as the
MgO 0.56 1.46 2.73
increases of effective w/c reducing the early strength, and it can SO3 1.90 <0.01 0.07
partly be compensated by the stimulation effect of clinker phases. K2O 1.07 5.60 4.25
The pozzolanic reaction of kaolinite calcined clay contributes after Na2O 0.05 0.08 1.61
few days [21,22] while its occurs after two weeks for calcined shale TiO2 – 0.76 0.89
P2O5 – 0.09 0.13
reducing the large capillary pores and improving the mechanical BaO – 0.09 0.06
strength and durability of blended cements [23–25]. Cr2O3 – 0.05 0.02
In this study, the performance of blended cements formulated MnO – 0.01 0.08
using two new calcined natural pozzolans obtained by calcination SrO – 0.01 0.01
LOI 1.90 0.58 0.81
of illitic shale locally available was analyzed. These cements are
developed for general use (GU) and delivery in bags for a low tech- Mineralogical composition [%]
C3S 59.1 – –
nological concrete use in developing countries. These blended
C2S 14.0 – –
cements require low water demand, adequate development of C3A 2.6 – –
strength and stability of hydrated products. For this purpose, the C4AF 14.0 – –
packing density, water film thickness, flowability, hydration kinet- Gypsum 4.8 – –
ics and strength development were conducted to understanding Calcite 3.2 –
Amorphous alumina-silica % – 56 49
the behavior of these calcined pozzolans and their application in Quartz – 35 31
the development of low-energy and low-carbon binders. According Illite dehydrated – 4 –
to the USGS Mineral commodity summaries 2020 [26], the world Feldspars – – 18
resources of all clays are extremely large, and the principal uses Hematite – 5 2
Hercynite – – 1
of common clays are to produce brick, lightweight aggregate, and
 G. Marchetti et al. / Construction and Building Materials 254 (2020) 119042 3

pressive strength. A total of six blended cement were obtained

by replacement 15, 25, and 35% of OPC by MI1 or MI2 by mass of
the total cementitious materials. The mix proportions of pastes
and mortars are reported in Table 2.

2.3. Packing density and WFT

Fig. 1. Particle size distributions of OPC, MI, MI2, and FA.
shown in Fig. 1. The median particle size (d50) was 19.65, 8.76,
12.74 and 450 lm for OPC, MI1, MI2 and FA, respectively.
To disperse the particles in paste and mortar mixtures, a
polycarboxylate-based superplasticizer (SP) with a solid mass con-
tent of 35% and a relative density of 1.03 g/cm3 was used.
2.2. Test program and mixture proportions
The first part of the test program was to measure the packing
density of materials (OPC, MI1, MI2 and FA), to predict the packing
density of blended cement pastes and mortars with MI1or MI2 and
to calculate the WFTs at different w/cm. The second part was to
analyze the flowability, the heat of hydration, the progress of
hydration, and the pore size distribution of blended cement pastes.
The third part of experimental tests was aimed to measure the
flowability and the compressive strength of mortars. Based on
the calculated WFT sand the results obtained in the second and
third parts of the experimental program, the effects of packing
density and WFT on the flowability are discussed. The dilution,
stimulation, and pozzolanic effects in hydration of blended cement
caused by illitic calcined shale are discussed to validate the com-
The packing density (u) of OPC, MI1, MI2, and FA was measured
with a SP dosage of 1.5% (by mass of cementitious materials) using
the wet packing method [13]. The packing density of blended
cement pastes and mortars was predicted by the CPM [30] and
the WFT was calculated at w/cm varied from 0.4 to 0.8 by mass.
Basically, u was determined as the maximum solid concentra-
tion obtained varying the amount of water in the mixture from
insufficient to more than sufficient to fill the voids between the
particles. The WFT represents the average thickness of water film
around the particles [31,19], and was obtained dividing the excess
water ratio (ew) by surface area (SA) of particles in the mixture. In
previous work [20], complete details of the method and the predic-
tion model are given.
The minimum voids ratio umin can be evaluated as:
1u
umin ¼ ð1Þ
u
From the voids ratio, the excess water ratio ew can be obtained
ew ¼ uw  umin ð2Þ
where uw is the w/s (defined as the ratio of the volume of water to
the volume of the particles). On the other hand, the surface area of
particles SA can be calculated as
SA ¼ SAOPC  ROPC þ SAMI1  RMI1 þ SAMI2  RMI2 þ SAFA  RFA ð3Þ
in which SAOPC, SAMI1, SAMI2, and SAFA are the surface areas of
cement, calcined shale and fine aggregate, and ROPC, RMI1, RMI2,
and RFA are the volumetric ratios of cement, calcined shale, and fine
aggregate to the total solid volume. With ew and SA so determined,
the WFT may be obtained as
ew
WFT ¼ ð4Þ
SA
2.4. Flowability
The flowability of cement pastes and mortars was measured
with SP dosage of 1.5% by mass of cementitious materials. For
cement paste, the mini slump test using the Kantro‘s cone (top
Ø = 19 mm; bottom Ø = 38 mm and height = 57 mm) [32] having

Table 2
Mix proportion of blended cement pastes and mortars.

Samples Dosage of each ingredient (kg/m3)

OPC MI1 MI2 Fine aggregate Water SP
OPC 1243.0 – – – 602.9 18.65
0.15MI1 1044.7 184.4 – – 596.1 18.44
0.25MI1 915.0 305.0 – – 591.7 18.30
0.35MI1 787.2 423.9 – – 587.4 18.17
0.15MI2 1047.2 – 184.8 – 597.5 18.48
0.25MI2 918.5 – 306.2 – 594.0 18.37
0.35MI2 791.4 – 426.1 – 590.5 18.26
M-OPC* 520.4 – – 1561.2 250.4 7.75
M-0.15MI1 436.9 77.1 – 1541.9 249.3 7.71
M-0.25MI1 384.3 128.1 – 1537.1 248.5 7.69
M-0.35MI1 332.0 178.8 – 1532.3 247.7 7.66
M-0.15MI2 437.3 – 77.2 1543.4 249.5 7.72
M-0.25MI2 384.9 – 128.3 1539.6 248.9 7.70
M-0.35MI2 332.8 – 179.2 1535.8 248.3 7.68

* M stands for mortar with cm/FA = 1/3.

4 G. Marchetti et al. / Construction and Building Materials 254 (2020) 119042

the same proportions as the slump cone of ASTM C 143 [33] was
carry out. After mixing, the paste was poured into the cone cen-
tered on polished steel plate until it was full, the cone was gradu-
ally lifted and after few seconds, two orthogonal diameters of the
paste-patty formed was measured and the flow spread was deter-
mined as the average diameter minus the bottom-Ø cone. For mor-
tars, the flow table test specified in ASTM C 230 [34] standard was
followed.
2.5. Heat of hydration, hydration compounds and pore size
distribution
The rate of heat released during hydration of the examined
pastes (w/cm = 0.50) was measured in a conduction calorimeter
under isothermal conditions at 20 °C during 48 h. To study the pro-
gress of hydration and the development of pastes structure, the
paste (w/cm = 0.50) of OPC, 0.25MI1 and 0.25MI2 were prepared
and cured in sealed plastic bags at 20 °C for 2, 7, 28 and 90 days.
At this time, the fragments of paste samples were immersed in iso-
propyl alcohol, dried and ground to particle size lower than 45 mm.
The crystalline compounds were identified by XRD on X́Pert Philips
PW 3710 diffractometer (CuKa radiation at 40 kV and 20 mA). The
combined TG-DSC analysis was performed on a Labsys Evo
(Setaram) apparatus from 25 °C to 1000 °C. The ground sample
was placed into an alumina crucible with a volume of 100 mm3,
the applied heating rate was 5 °C/min and the measurement was
conducted in an inert atmosphere. Pore size distribution was mea-
sured on a mercury porosimetry principle using devices Pascal 140
and Pascal 440 (Thermo Scientific) measuring the 4–100 lm and
the 3–4000 nm pore radium. Before the measurement, the samples
were dried at vacuum drier. The sample mass was ~2 g, whereas
the ungrounded specimens maintaining their unique structure
and morphology were tested.
ratio which increases with the OPC replacement and is also greater
for pastes with MI1.
For blended cement mortars (Fig. 2b), the incorporation of MI1
and MI2 increased the packing density of M-OPC (0.743) for all the
replacements, reaching values of 0.749 and 0.747 for 15%, 0.753
and 0.749 for 25% and 0.756 and 0.751 for 35% OPC replacement
with MI1 and MI2, respectively. These increases were due to the
combination of the cementitious materials used (OPC and MI1/
MI2) filling the voids between the FA particles achieving a denser
arrangement. The fact that the packing density of blended mortars
was improved, which was not the case of packing density of
blended cement pastes, could be due that the calcined clay was
added as a cement replacement by mass. As the calcined clay has
a lower density, when added to replace an equal mass of cement,
the total volume of powder (cement plus calcined clay) was
increased. It means it was the increased powder volume that
increased the packing density of mortars.
The incorporation of MI1 enabled reaching higher values of
packing density than when MI2 was incorporated; this may be
due to the fact that the particle size distribution of MI2 was closer
to that of the OPC, and therefore its filling effect was not as effec-
tive as that of MI1. There was also a greater decrease in the mini-
mum voids ratio for mortars with MI1.

2.6. Compressive strength

To measure the compressive strength, the standard mortars

specimens (w/cm = 0.5 by mass; cm/FA = 1/3) were cast, com-
pacted and kept in the laboratory during the first 24 h, demolded
at one day after casting, and cured in water at 20 ± 2 °C until the
age of testing. The mortar prisms (40 mm  40 mm  160 mm)
were tested at 2, 7, 28, and 90 days of maturing in accordance with
the standard EN 196-1 [29].

3. Results and discussion

3.1. Packing density and WFT

The packing density and the minimum voids ratio of the

blended cement pastes and mortars calculated by CPM are pre-
sented in Fig. 2. For blended cement pastes (Fig. 2a), it was
observed that the incorporation of MI1 or MI2 decreases the pack-
ing density of OPC paste (0.636) for all the replacements analyzed.
This may be due to the fact that these ground calcined shales had a
particle size distribution similar to OPC, so the filling effect was
slight, added to the fact that their packing densities were lower
than that of OPC (0.586 and 0.592 for MI1 and MI2, respectively).
As occur in aggregates [35], the particle shape is other parameter
that affects the packing density. Fig. 3 shows SEM micrographs
for OPC, MI and MI2 particles. OPC particles are irregularly shaped
with high angularity and chamfered edges, while MI1 and MI2 con-
tains some thin plates particles with frayed edges. The angularity
of particles may affect the frictional forces between the particles
and the aspect ratio (flakiness) of particles can reduce the packing
density. These effects can also be observed in the minimum voids Fig. 2. Packing density of blended cement: (a) pastes and (b) mortars.
 G. Marchetti et al. / Construction and Building Materials 254 (2020) 119042 5

Fig. 3. SEM micrographs of OPC, MI1, and MI2 particles.

When a SCM is incorporated, it can increase not only the pack-

ing density but also increase the surface area of the solid particles,
and for the same amount of excess water, decrease the average
thickness of water that coating the particles. To take into account
these two opposite effects, the WFT of blended cement pastes
and mortars was calculated and it is presented in Fig. 4. Although
the WFT was calculated from the w/cm by volume, in Fig. 4 it is
plotted against w/cm by mass that is more commonly used.
The WFT against w/cm curves are all straight lines because the
WFT is a linear function of the w/cm. Comparing the OPC paste
with those containing illitic calcined shale (Fig. 4a), it can be seen
that the WFT decreased with the incorporation of MI1 and MI2 for
all replacements. It was because the addition of MI1 and MI2
decreased the packing density of OPC and at the same time
increased the specific surface area (622 and 507 m2/kg for MI1
and MI2, respectively). Therefore, their incorporation to fill the
gaps between the OPC cement particles was not effective.
For the cement mortars, the WFT was calculated from the w/s
by volume (w/s includes cementitious materials and fine aggre-
gate) but was also plotted against the w/cm by mass (Fig. 4b). It
is observed that the WFT ranged from 0.268 mm to 0.787 mm.
All the WFT values were negative for the w/cm of 0.4, because
the amount of water was not enough to fill the gaps between the
solid particles. For w/cm of 0.5, the M-OPC had a negative WFT,
while mortars with MI1 and MI2 had positive values for all replace-
ments. The increase in the WFT was generally larger for a low w/
cm and became smaller as the w/cm increased. This was because
the WFT was governed by both the excess water ratio and the total
surface area. The proportional increase in excess water ratio due to
the addition of illitic calcined shale was larger at a lower w/cm, but
smaller at a higher w/cm, whereas the proportional increase in
total surface area was independent on the w/cm. As can be seen,
for w/cm lower than 0.6, the addition of up to 35% of MI1 or MI2
increased the WFT with respect to the M-OPC; while for higher
w/cm, the WFT begun to decrease due to the increase in the surface
area that predominated over the increase in excess water. In gen-
eral, it was observed that the incorporation of MI1/MI2 signifi-
cantly affected the packing density, the surface area and the
WFT. Although the incorporation of MI1 or MI2 did not improve
the packing density of cement paste for any replacement, it was
improved when they are added into mortars.

3.2. Flowability

Fig. 5 shows the flowability of pastes (Fig. 5a) and mortars

(Fig. 5b) plotted against the replacement percentage of MI1/MI2.
In Fig. 5a, the flowability decreased with the increasing replace-
ment of MI1/MI2 in paste. This was in agreement with the packing
results that showed that the incorporation of MI1 and MI2 not Fig. 4. WFT plotted against w/cm by mass for: (a) pastes and (b) mortars.
6 G. Marchetti et al. / Construction and Building Materials 254 (2020) 119042

3.3. Heat of hydration, hydration compounds and pore size

distribution

Fig. 6 shows the heat release rate curve for OPC paste and
cement pastes with 15%, 25% and 35% replacement by MI1
(Fig. 6a) and MI2 (Fig. 6b).
In Fig. 6a a first stage can be observed with a high rate of heat
released due to the initial hydrolysis and the reaction of the alu-
minum phase (formation of the AFt phase). This rate decreased
with the first minimum at approximately 200 min with intensity
of 0.11, 0.28, 0.25 and 0.19 mW/g for OPC, 0.15MI1, 0.25MI1, and
0.35MI1 pastes, respectively. After the first minimum, the particu-
lar slopes were similar and the second maximum occurred at the
same time (800 min) for all pastes with intensity of 1.01, 1.21,
1.11, and 1.01 mW/g for OPC, 0.15MI1, 0.25MI1, and 0.35MI1
pastes, respectively. The third peak occurred at 1000 min for OPC

Fig. 5. Flowability of blended cements: (a) pastes and (b) mortars.

effectively filled the gaps between the OPC particles, and thus,
there was no increase in the WFT to lubricate the particles
(Fig. 4a). The flowability values were slightly lower in pastes con-
taining MI1, because it had a surface area greater than MI2. There-
fore, the WFT values of pastes with MI1 were lower than those
containing MI2. Hence, flowability decreased with the incorpora-
tion of MI1/MI2, due to the decrease in WFT values.
The flowability of mortars (Fig. 5b) containing MI1/MI2 was for
all replacements higher than the flowability of M-OPC. The incor-
poration of both illitic calcined shales improved the flowability of
M-OPC as expected, due to the increase in WFT as it can be seen
in Fig. 4b for a w/cm of 0.50. However, the increase in flowability
was reduced with the increase in the replacement percentage.
From the above, it can be concluded that the flowability in both,
pastes and mortars, is highly dependent on WFT. In other words,
the WFT is the key factor that governs the flowability. Fig. 6. Rate of heat of hydration of blended cement pastes with (a) MI1 and (b) MI2.
 G. Marchetti et al. / Construction and Building Materials 254 (2020) 119042
Fig. 7. Relative total heat released per Portland cement gram of blended cement
pastes at 48 h.
Fig. 8. XRD patterns of cement pastes at 2, 7, 28, and 90 days.
7
paste (1.00 mW/g) and at 1000, 1025, and 1050 min for 0.15MI1
(1.24 mW/g), 0.25MI1 (1.20 mW/g), and 0.35MI1 (1.12 mW/g)
pastes, respectively. Finally, the period of deceleration of the reac-
tions took place until 48 h, at which time the test was finished.
It can be seen that due to a stimulation effect the heat release of
cement pastes with MI1 was greater than that of the OPC paste.
The highest value was recorded when the OPC replacement was
15%, and the heat release was lower as the replacement level
increased. It was also observed that the third peak was more
increased than the second peak. This increase was greater with
the increase of the replacement percentage (0.01 mW/g for
OPC, 0.03 mW/g for 0.15MI1, 0.09 mW/g for 0.25MI1, and
0.11 mW/g for 0.35MI1). This evidence could indicate a selective
stimulation of the aluminum phase.
In Fig. 6b, the first minimum had a similar occurrence time for
all pastes (200 min.) with the decreasing intensities for the
higher replacement percentages (0.22, 0.12, and 0.026 mW/g for
0.15MI2, 0.25MI2, and 0.35MI2 cement pastes, respectively). It
can be seen that the 0.15MI2 cement paste reached a higher inten-
sity than that corresponding to the OPC paste. It was due to the
stimulation effect, while for 0.25MI2 and 0.35MI2 pastes the dilu-
tion effect predominated.
The second peak occurred in all pastes with MI2 around
800 min, and its intensity decreased as the MI2 replacement
increased. Only the peak recorded for paste 0.15MI2 (1.17 mW/g)
exceeded the intensity of the OPC paste (1.01 mW/g). For the third
peak, the occurrence times were slightly in advance with respect to
8 G. Marchetti et al. / Construction and Building Materials 254 (2020) 119042
the OPC (1000 min), and its intensity decreased with the increasing
of cement replacement ratio; being 1.16 (1000 min), 0.87
(980 min), and 0.65 mW/g (965 min) for 0.15MI2, 0.25MI2, and
0.35MI2 pastes, respectively. The stimulation effect was observed
for the 0.15MI2 pastes, and the dilution effect predominated in
high replacement levels.
The relative total heat released per gram of OPC at 48 h is pre-
sented in Fig. 7. The heat released by cement pastes containing MI1
was always higher than that of OPC pastes and increased with the
replacement percentage. The total heat released by 0.15MI2 and
0.25MI2 cement pastes exceed heat released by OPC paste, while
the relative total heat released for 0.35MI2 was lower.
Fig. 8 shows the XRD patterns for OPC and blended cement
pastes with 25% replacement from 2 to 90 days. The OPC paste
showed ettringite (E) and calcium hydroxide (CH) as hydration
compounds at 2 days, accompanied with calcite (CC) and un-
hydrated phases (C4AF and C2S) from cement. For blended
cements, the hydrated products (E and CH) and unhydrated com-
pounds were the same as OPC; with additional quartz (Q) from cal-
cined shale. The AFm (hemicarboaluminate - Hc) was detected for
all cements at 7 days. For blended cements with MI1, the intensity
of CH peaks decreased at 28 days; but it had high intensity for
blended cement with MI2. The AFm transformation begun and
the monocarboaluminate (Mc) coexisted with Hc. Later, the Mc
was the predominant AFm phase. At 90 days, the CH was partly
Fig. 9. Differential scanning calorimetry (DSC) of cement pastes at 2, 7, 28, and 90 days.
consumed and judging by its peak intensity, the pozzolanic reac-
tion of MI2 is lower than the corresponding to MI1.
Fig. 9 shows the differential scanning calorimetry (DSC) curve
for hydrated cement pastes in mV at 2 (Fig. 8a), 7 (Fig. 8b), 28
(Fig. 8c), and 90 days (Fig. 8d). These curves show three main
endothermic heat flow peaks: a) from 100 °C to 250 °C the
recorded peak corresponded to the free and physically bound
water loss and the dehydration of ettringite, C-S-H, and AFm
phases [36,37]; b) from 410 °C to 520 °C the decomposition of cal-
cium hydroxide took place and c) from 650 °C to 800 °C the decom-
position of calcite (CaCO3) [36,38] and carbonated C-S-H [39] was
observed. Table 3 reports the relative mass changes obtained by
thermogravimetric analysis for the analyzed temperature range.
The mass loss at the temperature range 100–250 °C increased
with the age for all samples. For OPC, it was always greater than
that corresponding to blended cements, but the relative proportion
of mass loss decreased with the progress of hydration which indi-
cated the contribution of cement compounds derivate from the
pozzolanic reaction.
The mass loss attributed to CH decomposition (410–520 °C)
increased for all samples up to 28 days, and decreased at 90 days
for MI1 and MI2 samples. This revealed that the pozzolanic reac-
tion of illitic calcined clays consumed some part of CH at later ages.
The CH-reduction was more significant for MI1 blended cements
than for those with the same replacement of MI2. However, the
 G. Marchetti et al. / Construction and Building Materials 254 (2020) 119042 9

Table 3
Mass loss (%) at selected temperature range observed for OPC, MI1, and MI2 pastes.

Sample Temperature range Age (days)

2 7 28 90
OPC 100–250 °C 2.40 2.72 3.52 6.64
410–520 °C 4.21 4.27 5.17 6.17
650–800 °C 1.92 1.87 1.27 2.22
0.25MI1 100–250 °C 2.29 2.66 3.37 5.69
410–520 °C 2.22 3.07 3.99 3.22
650–800 °C 1.64 1.82 2.22 2.31
0.25MI2 100–250 °C 2.26 2.29 3.18 5.23
410–520 °C 3.26 3.54 4.22 3.97
650–800 °C 1.52 1.86 1.95 2.29

CH-content was always lower than that obtained from OPC which
was due to the dilution effect.
The carbonation of C-S-H led to the formation of vaterite, which
seems to be an unstable type of calcium carbonate which decom-
poses typically between 500 °C and 700 °C, at a lower temperature
than calcite [40]. The temperature range of the corresponding
decompositions was difficult to determine because the peaks were
overlapping. The peak temperature of the vaterite decomposition
was visible for samples analyzed at 7 and 28 days of ageing and
it was located approximately at 700 °C and 690 °C, respectively.
The peak temperature of the calcite decomposition was between
780 °C (for 2-days samples) and 730 °C (for 28-days samples).
These reactions were accompanied by a significant mass loss which
was approximately 1.6% at 2 days. Then it has increased with the
hydration time and reached approximately 2.0% at 28 days
(Table 3).
Fig. 10 shows the cumulative and volumetric pore size distribu-
tion measured for pastes at 2, 7, 28, and 90 days. The relative vol-
ume of pores for selected ranges of pore diameter is also shown in
this figure. At all investigated ages, the 0.25MI1 and 0.25MI2
pastes had a higher value of the total cumulative pore volume than
those of OPC. Moreover, the threshold pore diameter was reduced
for all samples with the increase of age, as expected.
At 2 days (Fig. 10a), the critical pore diameter (the pore size
with the highest frequency in the incremental volume curve) was
approximately 0.5 lm. At 7 days (Fig. 10b), the critical pore size

Fig. 10. Relative volume of pores by d.

10 G. Marchetti et al. / Construction and Building Materials 254 (2020) 119042

for 0.25MI1 and 0.25MI2 (~0.2 lm) was higher than that corre-
sponding to OPC (~0.06 lm); it was assigned to the prevailing dilu-
tion effect. At 28 and 90 days (Fig. 10c and d), the similar critical
pore size was monitored for all pastes (~0.06 lm) and it was also
observed an increase in the pore volume of small size (~0.01 lm)
for 0.25MI1 and 0.25MI2 paste indicating the pozzolanic effect of
illitic calcined shale.
In details of Fig. 10, the relative volume of pores size range is
reported. For macropores (100–1 lm), its volume was approxi-
mately constant at all ages. The volume of capillary pores ranged
from 1 to 0.1 lm was considerably reduced with the age of the
paste. Comparing the OPC and blended cements pastes, the dilu-
tion effect of calcined shale replacement caused a large volume
of capillary pores at early ages. The progress of pozzolanic reaction
led to the increased volume of finer pores (0.1–0.01 lm) attaining
to the volume larger than the corresponding to OPC at 7 days. From
28 to 90 days, the volume of very fine pores (0.001–0.01 lm) was
also increased for both blended cements.

3.4. Compressive strength

Fig. 11 shows the mortar compressive strength for MI1

(Fig. 11a) and MI2 (Fig. 11b) blended cements. In Fig. 11a, the com-
pressive strength of mortars containing MI1 at 2 days was 13.8,
11.2, and 9.1 MPa for 15, 25, and 35% replacements, and the OPC
mortar reached the compressive strength value of 17.7 MPa. At
7 days, the compressive strength of mortars with MI1 was lower
than that of M-OPC (35.8 MPa), and at 28 days, mortar M-
0.15MI1 (49.2 MPa) exceeded the strength of control mortar M-
OPC (46.6 MPa); while M-0.25MI1 and M-0.35MI1 reached the
compressive strength values of 44.9 and 40.9 MPa, respectively.
At 90 days, all mortars with MI1 exceed the strength of M-OPC
(53.7 MPa), reaching the highest value of 58.5 MPa for M-
0.15MI1 mortar.
This finding is highly promising for the use of this type of cal-
cined shale as SCM because most of the calcined clay such as cera-
mic dust are applicable in the lower amounts, typically in the range
10–20% of OPC mass taking into consideration particle size and
character of minerals forming the clay silicates [41].
At early ages (2 and 7 days), the compressive strength of mor-
tars with MI1 was lower than that of corresponding to control
mix M-OPC. It was owing to the dilution effect that was predomi-
nant due to the increase in the effective w/c, while from 28 days
samples the pozzolanic activity of the illitic calcined shale begun
to reveal resulting in the compressive strength of M-0.15MI1 mor-
tar higher than that of M-OPC. In this way, the reactivity of studied
shales in the presence of Portland cement hydrates was clearly
proven.
Fig. 11. Compressive strength of mortars with calcined shale: a) MI1 and b) MI2.
Mortars with MI2 (Fig. 11b) had lower compressive strength for
all replacements than those of M-OPC up to 28 days. At 90 days,
only mortar M-0.15MI2 exceeded the compressive strength of M-
OPC with a value of 55.6 MPa, and M-0.25MI2 reached a value sim- is ~1450 °C, which is much higher than that of calcined clays.
ilar to that corresponding to M-OPC. Therefore, a decrease in both CO2 production and energy consump-
In summary, due to the dilution effect the strength was lower as tion with the increasing dosage of calcined clays in cement blends
the replacement percentage increased. The lowest compressive can be anticipated. Based on the calcination technology, there are
strength was obtained for M-0.35MI2 which reached the lowest differences in CO2 emissions basically linked with the energy effi-
values at all studied ages, without exceeding the compressive ciency of the used kiln. Díaz et al. [42] reported on energy con-
strength of control mortar M-OPC. sumption and CO2 emissions of various calcination technologies.
The energy consumed for the production calcined clay varied from
3.5. Eco-efficiency of illitic blended cement 4223 MJ/t to 2734 MJ/t with the CO2 emissions in the range of 393–
196 kg/t. For these studied shales, the data of industrial pilot trials
The use of illitic clays calcined at 950 °C as partial Portland indicated an energy consumption of 2900–2750 MJ/t during calci-
cement substitute represents eco-efficient ‘‘green solution” for nation and the CO2 emission of 240–260 kg/t. On the other hand,
production of cement-based composites with reduced energy and the energy composition and CO2 emissions coming from OPC man-
carbon footprint. The clinkering temperature of Portland cement ufacturing are much higher (3230 MJ and 980 kg CO2eq/t) [43].
 G. Marchetti et al. / Construction and Building Materials 254 (2020) 119042
Specific thermal energy demand for production of Portland clinker
is also dependent on the applied production technology, i.e., dry
process, multi-stage cyclone preheater and pre-calcining kilns,
semi-dry/semi-wet processes, dry process with long kilns, dry pro-
cess rotary kilns equipped with cyclone preheaters, etc. For exam-
ple specific thermal energy demand for production of 1 t of
Portland clinker in dry process rotary kilns varies from 3100 MJ
to 4200 MJ [44]. Energy demand for clinkering using semi-dry
techniques varies from 3300 MJ to 5400 MJ [45]. So, the energy
savings by any partial cement replacement are quite apparent
and help ensure the sustainability of the concrete production with
equivalent engineering properties at later ages [47].
4. Conclusions
Two types of calcined illitic calcined shale were examined as
alternative low-energy and low-carbon SCMs. The effect of incor-
poration of these active alumino silicates into composition of
blended pastes and mortars was evaluated by the comprehensive
analysis of the packing density, kinetics of hydration, development
of hardened products, and mechanical strength. Based on the
results obtained in this study, the following main conclusions were
drawn:
The particle size distribution of MI1 and MI2 types calcined
shales was not the most appropriate to fill the gaps between the
OPC particles causing a decrease in the packing density. The
increase in the specific surface led to WFT values lower than those
of OPC paste for all replacements used (15 to 35%). Consequently,
paste flowability decreased with the incorporation of MI1 and MI2.
Unlike in pastes, the incorporation of MI1 and MI2 in cement
increased the packing density of OPC mortar. It was attributed to
the efficient filling effect between sand particles and the blended
cements (OPC+MI1/MI2). The WFT values increased compared
with the M-OPC up to w/cm of 0.6 and then it decreased. Therefore,
the flowability of mortars (w/cm = 0.5 by mass) increased with the
incorporation of MI1 and MI2. So, the packing results obtained for
pastes should not be extended to mortars since in the mortars it
should also be taken into account the particle size distribution of
the fine aggregate.
The heat of hydration showed that the MI1 blended cements
exceeded the dilution until 48 h for all replacement percentages,
and those containing MI2 only exceeded the dilution for 15% and
25% replacements. In addition, the pozzolanic action was also
demonstrated by the CH consumption in the XRD and DSC analysis,
especially for the MI1 blended cements; the decrease of the pores
in the range of 1–0.1 mm and in the increase of the finest pores (0.
1–0.01 mm)
In general, the compressive strength values of mortars contain-
ing MI1 were higher than those containing MI2. At 90 days, the
cement replacements of 15% and 25% with MI1 and MI2 reached
and/or exceed the strength of OPC mortar. Mortars designed with
up to 15% replacement exhibited similar behavior to the OPC mor-
tar from a rheological and mechanical point of view with the con-
sequent reduction in CO2 emissions.
CRediT authorship contribution statement
Guillermina Marchetti: Writing - original draft, Investigation,
Data curation. Viviana Rahhal: Investigation, Data curation,
Methodology, Formal analysis. Zbyšek Pavlík: Writing - review &
editing, Formal analysis. Milena Pavlíková: Investigation, Method-
ology, Data curation. Edgardo F. Irassar: Writing - review & edit-
ing, Conceptualization, Methodology, Formal analysis, Data
curation.
11
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
The authors gratefully acknowledge the financial support
received from CICPBA-CONICET under project PIO 004 and from
the Czech Science Foundation, under project No 18-18-07332S –
Properties, durability, and performance of lightweight mortars
with mineral admixtures.
References
[1] R. Fernandez, F. Martirena, K.L. Scrivener, The origin of the pozzolanic activity
of calcined clay minerals: a comparison between kaolinite, illite and
montmorillonite, Cement and Concrete Research 41 (1) (2011) 113–122,
https://doi.org/10.1016/j.cemconres.2010.09.013.
[2] A. Tironi, M.A. Trezza, A.N. Scian, E.F. Irassar, Potential use of Argentine
kaolinitic clays as pozzolanic material, Applied Clay Science 101 (2014) 468–
476, https://doi.org/10.1016/j.clay.2014.09.009.
[3] C. He, E. Makovicky, B. Øsbæck, Thermal stability and pozzolanic activity of
calcined illite, Applied Clay Science 9 (5) (1995) 337–354, https://doi.org/
10.1016/0169-1317(94)00033-M.
[4] R. Lemma, E.F. Irassar, V. Rahhal, Calcined illitic clays as Portland cement
replacements, in: K. Scrivener, A. Favier (Eds.), Calcined Clays for Sustainable
Concrete, RILEM Bookseries, vol. 10, Springer, Dordrecht, 2015, pp. 269–276,
doi: 10.1007/978-94-017-9939-3_33.
[5] C. He, B. Osbaeck, E. Makovicky, Pozzolanic reactions of six principal clay
minerals: activation, reactivity assessments and technological effects, Cement
and Concrete Research 25 (8) (1995) 1691–1702, https://doi.org/10.1016/
0008-8846(95)00165-4.
[6] N. Garg, J. Skibsted, Pozzolanic reactivity of a calcined interstratified illite/
smectite (70/30) clay, Cement and Concrete Research 79 (2016) 101–111,
https://doi.org/10.1016/j.cemconres.2015.08.006.
[7] J.J. Chen, A.K.H. Kwan, Superfine cement for improving packing density,
rheology and strength of cement paste, Cement and Concrete Composites 34
(1) (2012) 1–10, https://doi.org/10.1016/j.cemconcomp.2011.09.006.
[8] P. Banfill, Rheological methods for assessing the flow properties of mortar and
related materials, Construction and Building Materials 8 (1) (1994) 43–50,
https://doi.org/10.1016/0950-0618(94)90007-8.
[9] G. De Schutter, A.-M. Poppe, Quantification of the water demand of sand in
mortar, Construction and Building Materials 18 (7) (2004) 517–521, https://
doi.org/10.1016/j.conbuildmat.2004.04.004.
[10] B.V. Reddy, A. Gupta, Influence of sand grading on the characteristics of
mortars and soil–cement block masonry, Construction and Building Materials
22 (8) (2008) 1614–1623, https://doi.org/10.1016/j.conbuildmat.2007.06.014.
[11] G. Marchetti, E.F. Irassar, V.F. Rahhal, Effects of packing density and water film
thickness on fresh and hardened properties of ternary cement pastes,
Advances in Cement Research (2019) 1–12, https://doi.org/
10.1680/jadcr.18.00133.
[12] J. Kaufmann, F. Winnefeld, D. Hesselbarth, Effect of the addition of ultrafine
cement and short fiber reinforcement on shrinkage, rheological and
mechanical properties of Portland cement pastes, Cement and Concrete
Composites 26 (2004) 541–549, https://doi.org/10.1016/s0958-9465(03)
00070-2.
[13] H.H.C. Wong, A.K.H. Kwan, Packing density of cementitious materials: Part 1 -
measurement using a wet packing method, Materials and Structures/
Materiaux et Constructions 41 (4) (2008) 689–701, https://doi.org/10.1617/
s11527-007-9274-5.
[14] W.W.S. Fung, A.K.H. Kwan, H.H.C. Wong, Wet packing of crushed rock fine
aggregate, Materials and Structures/Materiaux et Constructions 42 (5) (2009)
631–643, https://doi.org/10.1617/s11527-008-9409-3.
[15] A.K.H. Kwan, W.W.S. Fung, Packing density measurement and modelling of
fine aggregate and mortar, Cement and Concrete Composites 31 (6) (2009)
349–357, https://doi.org/10.1016/j.cemconcomp.2009.03.006.
[16] A.H.K. Kwan, H.H.C. Wong, Effects of packing density, excess water and solid
surface area on flowability of cement paste, Advances in Cement Research 20
(1) (2008) 1–11, https://doi.org/10.1680/adcr.2008.20.1.1.
[17] H.H.C. Wong, A.K.H. Kwan, Rheology of cement paste: role of excess water to
solid surface area ratio, Journal of Materials in Civil Engineering 20 (2) (2008)
189–197, https://doi.org/10.1061/(ASCE)0899-1561(2008)20:2(189).
[18] A.H.K. Kwan, W.W.S. Fung, H.H.C. Wong, Water film thickness, flowability and
rheology of cement-sand mortar, Advances in Cement Research 22 (1) (2010)
3–14, https://doi.org/10.1680/adcr.2008.22.1.3.
[19] Y. Li, J.J. Chen, A.K.H. Kwan, Roles of water film thickness in fresh and hardened
properties of mortar, Advances in Cement Research 25 (3) (2013) 171–182,
https://doi.org/10.1680/adcr.12.00003.
12 G. Marchetti et al. / Construction and Building Materials 254 (2020) 119042
[20] G. Marchetti, V.F. Rahhal, E.F. Irassar, Influence of packing density and water
film thickness on early-age properties of cement pastes with limestone filler
and metakaolin, Materials and Structures 50 (2) (2017) 111, https://doi.org/
10.1617/s11527-016-0979-1.
[21] A. Tironi, M.A. Trezza, A.N. Scian, E.F. Irassar, Kaolinitic calcined clays: Factors
affecting its performance as pozzolans, Construction and Building Materials 28
(1) (2012) 276–328, https://doi.org/10.1016/j.conbuildmat.2011.08.064.
[22] A. Alujas, R. Fernández, R. Quintana, K.L. Scrivener, F. Martirena, Pozzolanic
reactivity of low grade kaolinitic clays: Influence of calcination temperature
and impact of calcination products on OPC hydration, Applied Clay Science 108
(2015) 94–101, https://doi.org/10.1016/j.clay.2015.01.028.
[23] S. Seraj, R. Cano, R.P. Ferron, M.C. Juenger, Calcined shale as low cost
supplementary cementitious material, in: K. Scrivener, A. Favier (Eds.).
Calcined Clays for Sustainable Concrete, RILEM Bookseries, vol. 10, Springer,
Dordrecht, 2015, pp. 531–537, doi: 10.1007/978-94-017-9939-3_66.
[24] E.F. Irassar, V.L. Bonavetti, C.C. Castellano, M.A. Trezza, V.F. Rahhal, G. Cordoba,
R. Lemma, Calcined illite-chlorite shale as supplementary cementing material:
thermal treatment, grinding, color and pozzolanic activity, Applied Clay
Science 179 (2019), https://doi.org/10.1016/j.clay.2019.105143 105143.
[25] E.F. Irassar, A. Tironi, V.L. Bonavetti, M.A. Trezza, C.C. Castellano, V.F. Rahhal, H.
A. Donza, A.N. Scian, Thermal treatment and pozzolanic activity of calcined
clay and shale, ACI Materials Journal 116 (4) (2019) 133–143, https://doi.org/
10.14359/51716717.
[26] U.S. Geological Survey, Mineral commodity summaries 2020: U.S. Geological
Survey, 2020, 200p, doi: 10.3133/mcs2020.
[27] ASTM C 188, Standard Test Method for Density of Hydraulic Cement, ASTM
International, West Conshohocken, PA, 2009.
[28] ASTM C 204, A Fineness of Hydraulic Cement by Air Permeability Apparatus,
ASTM International, West Conshohocken, PA, 2018.
[29] EN 196-1,, Methods of Testing Cement–Part 1: Determination of Strength,
European Committee for Standardization, Brussels, Belgium, 2005.
[30] F. De Larrard, Concrete Mixture Proportioning, CRC Press, London, 1999.
[31] A.H.K. Kwan, J.J. Chen, Roles of packing density and water film thickness in
rheology and strength of cement paste, Journal of Advanced Concrete
Technology 10 (2012) 332–344, https://doi.org/10.3151/jact.10.332.
[32] D.L. Kantro, Influence of water-reducing admixtures on properties of cement
paste–a miniature slump test, Cement, Concrete and Aggregates 2 (2) (1980)
95–102, https://doi.org/10.1520/CCA10190J.
[33] ASTM C 143,, Standard Test Method for Slump of Hydraulic-Cement Concrete,
ASTM International, West Conshohocken, PA, USA, 2005.
[34] ASTM C 230,, Standard specification for Flow Table for Use in Tests of
Hydraulic Cement, ASTM International, West Conshohocken, PA, USA, 2003.
[35] A.K.H. Kwan, C.F. Mora, Effects of various shape parameters on packing of
aggregate particles, Magazine of Concrete Research 53 (2001) 91–100, https://
doi.org/10.1680/macr.2001.53.2.91.
[36] W. Sha, E. O’Neill, Z. Guo, Differential scanning calorimetry study of ordinary
Portland cement, Cement and Concrete Research 29 (9) (1999) 1487–1489,
https://doi.org/10.1016/S0008-8846(99)00128-3.
[37] W. Sha, G. Pereira, Differential scanning calorimetry study of ordinary Portland
cement paste containing metakaolin and theoretical approach of metakaolin
activity, Cement and Concrete Composites 23 (6) (2001) 455–461, https://doi.
org/10.1016/S0008-8846(00)00472-5.
[38] L.P. Esteves, On the hydration of water-entrained cement–silica systems:
combined SEM, XRD and thermal analysis in cement pastes, Thermochimica
Acta 518 (1–2) (2011) 27–35, https://doi.org/10.1016/j.tca.2011.02.003.
[39] G. Villain, M. Thiery, G. Platret, Measurement methods of carbonation profiles
in concrete: thermogravimetry, chemical analysis and gammadensimetry,
Cement and Concrete Research 37 (8) (2007) 1182–1192, https://doi.org/
10.1016/j.cemconres.2007.04.015.
[40] A. Trník, L. Scheinherrová, T. Kulovaná, Z. Pavlík, V. Rahhal, E.F. Irassar, R.
Černý, Thermogravimetry of Portland Cement from Argentina and Czech
Republic, Advanced Materials Research 1126 (2015) 169–173, https://doi.org/
10.4028/www.scientific.net/AMR.1126.169.
[41] V.F. Rahhal, M.A. Trezza, A. Tironi, C.C. Castellano, M. Pavlíková, J. Pokorný, E.F.
Irassar, O. Jankovský, Z. Pavlík, Complex characterization and behavior of
waste fired brick powder-Portland cement system, Materials 12 (10) (2019)
1650, https://doi.org/10.3390/ma12101650.
[42] Y. Cancio Díaz, S. Sánchez Berriel, U. Heierli, A.R. Favier, I.R. Sánchez Machado,
K.L. Scrivener, J.F. Martirena Hernández, G. Habert, Limestone calcined clay
cement as a low-carbon solution to meet expanding cement demand in
emerging economies, Development Engineering 2 (2017) 82–91, https://doi.
org/10.1016/j.deveng.2017.06.001.
[43] S. Çankaya, Investigating the environmental impacts of alternative fuel usage
in cement production: a life cycle approach, Environmental Development and
Sustainability (2019), https://doi.org/10.1007/s10668-019-00533-y.
[44] J.A. Moya, N. Pardo, A. Mercier, Energy efficiency and CO2 emissions:
prospective scenarios for the cement industry, JRC of Scientific and Technical
Reports, Publications Office of the European Union, https://ec.europa.eu/jrc/
en/publication/eur-scientific-and-technical-research-reports/energy-
efficiency-and-co2-emissions-prospective-scenarios-cement-industry
(accessed February 21, 2020), 2010, doi: 10.2790/25732
[45] F. Schorcht, I. Kourti, B.M. Scalet, S. Roudier, L. Delgado Sancho, Best available
techniques in the cement, lime and magnesium oxide manufacturing
industries, European Commission JRC-IPTS, https://eippcb.jrc.ec.europa.eu/
reference/production-cement-lime-and-magnesium-oxide (accessed February
21, 2020), 2013, doi: 10.2788/12850
[46] G.P. Cordoba, S.V. Zito, R. Sposito, V.F. Rahhal, A. Tironi, C. Thienel, E.F. Irassar,
Concretes with calcined clay and calcined shale: workability, mechanical and
transport properties, Journal of Materials in Civil Engineering (2020), https://
doi.org/10.1061/(ASCE)MT.1943-5533.0003296.
[47] M. Pavlíková, L. Zemanová, J. Pokorný, M. Záleská, O. Jankovský, M. Lojka, D.
Sedmidubský, Z. Pavlík, Valorization of wood chips ash as an eco-friendly
mineral admixture in mortar mix design, Waste Management 80 (2018) 89–
100, https://doi.org/10.1016/j.wasman.2018.09.004.