MATEC Web of Conferences 364, 05014 (2022) https://doi.org/10.

1051/matecconf/202236405014
ICCRRR 2022

Feasibility of using clays from Southeast European deposits in

limestone calcined clay cements
Matea Flegar1, Marijana Serdar1,*, Diana Londono-Zuluaga2 and Karen Scrivener2
1University of Zagreb, Faculty of Civil Engineering, Department of Materials, Zagreb, Croatia
2Laboratory of Construction Materials, Ecole Polytechnique Fédérale de Lausanne, Lausanne, Switzerland

Abstract. Recently, the cement industry has faced new challenges in addition to the environmental
constraints of the last decade. The decline in availability and current inconsistent prices of common
supplementary cementitious materials (SCMs), such as by-products from the iron industry or coal-fired
power plants, have opened the search for more reliable materials. Research on cements containing calcined
clays now serve as a possible solution to the forementioned problems. Clays containing the mineral
kaolinite in sufficient quantities, when calcined and mixed with limestone powder, produce hydration
products that can improve the strength and durability of concrete. In addition, the production of limestone
calcined clay is reported to be less CO2 intensive, but this eco-efficient solution is viable only if the
materials are locally available. For this reason, this study investigates the possibility of using natural clays
from the Southeast European region (SEE) as cement replacements. A systematic experimental study was
conducted on 18 different clays from 13 different deposits to determine the physical and mineralogical
composition of the raw clays, their reactivity and mortar strength. The results were then related to the
environmental contributions they might have in comparison with ordinary Portland cement in concrete.

1. Introduction such as quartz, feldspars, mica, calcite and others [4].

Supplementary cementitious materials are siliceous
and aluminous materials that serve as cement
replacements in concrete. Most commonly used SCMs
are by-products from industry such as steel slag or fly
ash from burning coal. In western EU countries
majority of those resources is being rapidly depleted as
we move to more ecological energy resources and
increase the recycling of steel [1]. While majority of
CO2 emissions come from the production of clinker,
the use of alternative SCMs such as calcined clays
serve as most favourable solutions in reaching carbon
neutrality by 2050 [2].
The reactivity of clays in cements is led by their
possibility of amorphization, i.e. the dehydroxylation
of the clay minerals which makes them pozzolanic.
Kaolinite is the most advantages clay mineral with a
1:1 silica and alumina layer formation. This structure
allows a more easy decomposition of the hydroxyl
groups than in the case of a 2:1 layer minerals such as
illite or montmorillonite [3]. In nature, clays are found
in different forms and with different mineralogical
compositions, mostly containing mineral illite,
kaolinite and montmorillonite but also other impurities
Even though kaolinite requires the lowest calcination
temperature (500-800°C), other minerals can exhibit
pozzolanic properties with a suitable temperature [3].
Studies have shown that even a medium range kaolinite
content of about 50% can obtain comparable
compressive strength results to OPC mixes after only 7
days with a clinker substitution of 45% (30% calcined
clay and 15% limestone) [5]. It is outlined in the study
that calcined clays can subitise Portland cement with a
major cost and energy reduction during production due
to the lower calcination temperature.
This study is a part of a project aimed to investigate
suitable ecological and low-cost calcined clay
cementitious materials, containing local low grade
kaolinite clays for the development of alternative
binders. By screening regionally available clay
materials for the use as SCMs a more comprehensive
conclusion can be drown out regarding their feasibility.
It is also crucial to find a relationship between
properties of different natural clays and its performance
in concrete, not only for understanding the interaction
with cement, but also to address the durability and
strength development.

*Corresponding author: marijana.serdar@grad.unizg.hr

© The Authors, published by EDP Sciences. This is an open access article distributed under the terms of the Creative Commons Attribution License 4.0
(http://creativecommons.org/licenses/by/4.0/).
MATEC Web of Conferences 364, 05014 (2022) https://doi.org/10.1051/matecconf/202236405014
ICCRRR 2022

2. Materials and methodology 9

OPC
Q
8
MAR
This study evaluates 18 different natural clay 7 Cu1
Cu2
samples taken from 13 different deposits. All materials 6 ILO

originate from the Southeast Europe region and were ORA

Volume (%)
TOP1
5
collected as a part of the “Advanced low CO2 TOP2
KaVa1
cementitious materials, ACT” project. 4
KaVa2

Before characterisation and testing all materials were 3

dried in an oven for 24 ± 2 h at 60 ± 5°C and then 2

grinded in a disc mill for 30 seconds. 1

0
0.01 0.1 1 10 100 1000
Particle size (um)
9
OPC
8 Q
NC1
7 NC2
SLVK
6 GM

Volume (%)
K1
5 K3
K5
4 ZOR
D2
3

Fig. 1. Map of the clay excavation points and distances 2

from one cement plant 1

Characterisation of raw materials was performed in 0

0.01 0.1 1 10 100 1000
the Laboratory of Construction Materials at EPFL Particle size (um)

while the mortar properties were tested on the Faculty

of Civil Engineering, University of Zagreb. Fig. 2. Particle size distribution of dry and grinded clay
samples, quartz and Portland cement determined by

2.1. Characterisation methods The solvent was chosen according to the

The chemical composition of the selected materials
was determined by X-ray fluorescence (XRF) (Fig. 3).
The density of particles after drying was measured by
Le Chatelier flask method according the ASTM C188-
17 standard [6]. The particle size distribution (PSD)
was was determined using the Mastersizer 2000
instrument with a wet laser diffraction procedure by
dispersing the particles in different solvents depending
on the material type.
recommendations from Scrivener et.al. (2016) [7],
0.01wt.% polyacrylic acid for clay testing, isopropanol
for cement and water for quartz. Results of the PSD are
shown in the Fig. 2.The mineralogical composition was
studied using thermogravimetric analysis (TGA) and
X-ray diffraction (XRD). TGA was performed with
TGA/SDTA 851 apparatus (Mettler Toledo, Columbus,
OH, USA).

100

90

80

70
Composition (%)

60

50

40

30

20

10

CaO SiO₂ Al₂O₃ Fe₂O₃ MgO P₂O₅ Na₂O K₂O TiO₂ MnO SO₃
Fig. 3. Chemical composition of clay samples compared to the Portland cement

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MATEC Web of Conferences 364, 05014 (2022) https://doi.org/10.1051/matecconf/202236405014
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Samples of 50 ± 5 mg of materials were heated developed for the RILEM TC-267 committee, was
from 30 °C to 1000 °C, with a constant heating rate of caried out using isothermal calorimetry, obtaining the
10 °C and a nitrogen flow of 30 mL/min. The resulting total 7-day heat release at 40°C of pastes composed of
DTG curves were used to calculate the kaolinite the SCMs. Prior to the test, all the SCMs and reagents
content as the primary indicator of pozzolanic were weighted, mixed and held at 40 ± 2 °C for 24 h.
properties of clays. The formulation of the solid blends relies on the ratio
The amount of kaolinite was calculated according of Ca(OH)2/SCM and CaCO3/SCM of 3 and ½
to the weight loss between approximately 350 and respectively. In addition, an alkali solution 3M of K
650°C (WLdehydroxylation), using the molecular were prepared with KOH and K2SO4.
masses of kaolinite [7], according the “Eq (1)”. The
weight loss for this calculation was obtained with the 450

tangent method. ~40 % Kaolinite

Error! Reference source not found. 400

Kaolinite (%) = WLdehydroxylation × (258/36) (1) 350

~30 % Kaolinite MAR
CU_1
300 CU_2
X-ray diffraction (XRD) was used for ILO

< 25 % Kaolinite ORA

Heat (J/g SCM)

quantification of amorphous content using the Philips 250
TOP_1
TOP_2

X‘Pert Pro (Malvern Panalytical, Malvern, UK), θ-θ 200

KAVA_1
KAVA_2

configuration, wavelength CuKα1,α2. Powder patterns 150

NC_1
NC_2
SLVK
were recorded between 5 and 70° 2θ range, with 0.002° IGM
100 K1
2θ step size and a sampling time per step of 30 s. K3
K5

X’Pert HighScore Plus software (v3.0e, Malvern 50

ZOR
D2

Panalytical, Malvern, UK) was applied for mineral 0

0 20 40 60 80 100 120 140 160

phase identification and Rietveld refinement. For Time (h)

amorphous quantification high crystalline rutile was Fig. 5. Reactivity test (R3) results for clay samples
used as external standard method.
-0.0001
The pastes were prepared in a high shear mixer at
100

-0.0007
1600 ± 50 rpm for 2 min until get a homogenous paste.
Immediately, they were cast in glass vial and placed
into the isothermal calorimeter
98 -0.0013

-0.0019
Mass loss (%)

DTG (mgs^-1)

96
-0.0025
Dehydroxylation of
kaolinite/illite 2.3. Mortar strength
-0.0031
MAR

Prior mixing of mortars all clays have been

94
CU_1
-0.0037
CU_2
ILO
ORA -0.0043
calcinated in a furnace at 800°C for 1 h. In this study,
92 TOP_1
Top_2
20 mortar mixtures have been considered, in which the
-0.0049
KaVa_1
KaVa_2
water to binder ratio and the content of total binder was
90
40 140 240 340 440 540 640 740 840 940
-0.0055
0.5 and 450 kg/m3, respectively. Portland cement CEM
Temperature (°C) 1 45.2 R was used for the reference sample (OPC) and
101 the mixes with SCMs. Binary blended mortars
99
-0.0004
consisted of 70% of OPC + 30% of calcined clays and
one mixture with 30% of quartz powder. Standardized
-0.0012

-0.002
97
Decomposition of
-0.0028
sand was used as aggregate and polycarboxylate (PCE)
CaCO3

95 -0.0036
was added to obtain adequate workability (up to 1% on
Mass loss (%)

weight of binder). For each mixture, a volume of 1,5

DTG (mgs^-1)

-0.0044
93
-0.0052 litre was mixed following the norm EN 196-1 (2016)
91 NC_2 -0.006 [8], after which samples of 40 x 40 x 160 mm were
NC_1
SlVk
-0.0068
cast. The Samples were covered with a plastic wrap
IGM
after casting and held 24 h in laboratory conditions.
89
-0.0076
K1
K3
87 K5
ZOR
Dehydroxylation of
kaolinite/illite
-0.0084
When demoulded they were cured in humidity chamber
-0.0092

85
D2
-0.01
(RH 95%) until testing time. Compressive strength test
40 140 240 340 440 540 640 740 840 940
was carried out on 2 prisms after 2, 7 and 28 days of
Temperature (°C) curing age, according to the norm mentioned above.

Fig. 4. Mass loss and DTG curve for each clay sample
2.4. Life cycle assessment

2.2. Pozzolanic reactivity The LCA was performed according to the ISO
14044:2016 standard [9] to compare the environmental
The R3 test was caried out to assess the possible impact of two different cement productions. Label
pozzolanic properties of collected material. This test, CEM I indicate a mix of cement clinker with 6% of

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MATEC Web of Conferences 364, 05014 (2022) https://doi.org/10.1051/matecconf/202236405014
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gypsum while the LCC shows a mixture of limestone The evaluated impact categories were abiotic
calcined clay cement contains 50% clinker, 30% depletion potential (ADP), acidification potential (AP),
calcined clay, 15% limestone and 5% gypsum. The eutrophication potential (EP), global warming potential
binders were modelled with a cradle-to gate approach (GWP) and photochemical oxidation potential (POP).
(Fig. 6), taking into account the material acquisition, The choice of impact categories is based on a study
preparation and transport. The inventory data for the that indicates categories mostly affected by the
cement productions were taken from the Ecoinvent production of blended cements [11]. This includes raw
database, obtaining the realistic distances from raw material excavation, use of fossil fuels, transport,
material acquisition to the cement plant ( electricity, and the atmospheric emissions from the
Fig. 1). cement kiln.

Raw material extraction

at the plant
Raw material extraction
sand, iron ore
3. Results and discussion
Limestone Clay
Raw material transport
The chemical composition of clays differs from the
System boundary: sand, iron ore OPC, having a much higher silica and alumina amount.
Cradle – to -gate
The biggest difference between clays is the
Raw meal production
Grinding, mixing, etc.
alumina/silica ratio and the amount of iron oxide. The
particle size distribution of clays is somewhat similar
Clinker production to the Portland cement, having a higher amount of
Preheating, rotary kiln, clinker cooling, clinker
storage
Gypsum
Extraction,
smaller particles in the range of 0,1 to 1. The outputs of
transportation the TG measurement indicate the kaolinite content of
each sample (Table 2). The range goes from 9.7 to as
high as 43.1 %, meaning the clays from this region can
L
Mixing and
blending
Mixing and
blending CC
be categorised as low and medium range kaolinitic
clays. The DTG curve also shows peaks around the
CEM I LCC temperature of 740°C which is a typical peak that
describes the decomposition of limestone (CaCO3)
Fig. 6. System boundary for CEM I and LCC production [13]. Clays NC1 and K3 have a distinct peak in that
area.
The inventory input/output data is shown in the
Table 1. The functional unit (FU) chosen for this study Table 2. Characterisation results of density measurement,
was one kg of cement binder that is assumed to be used TGA and XRD
for standard concrete strength production. For the Life
Density Kaolinite Amorphous
Cycle Impact assessment characterisation factors were content content of
dry
adopted from the CML database developed by the Label obtained raw clays
Centrum voor Milieuwetenschappen Leiden [10]. [g/cm3] by TGA obtained by
(%) XRD (%)
Table 1. Inventory data for the LCA of CEM I and LCC
MAR 2.26 17.6 14.4
Description Reference CU_1 2.59 11.6 16
data CU_2 2.43 10.8 15.2
ILO 2.29 19.1 10.9
Material
ORA 2.56 9.7 1.2
Clinker – preparation of raw material
TOP_1 2.52 13.5 47.1
(exploitation, fuel preparation and
TOP_2 2.5 16.4 4.6
calcification)
Ecoinvent KaVa_1 2.57 15.2 7.7
Calcined clay - exploitation of raw
database KaVa_2 2.57 13.8 8.2
material, fuel and calcination (500-900°C)
NC_1 2.12 13.4 11.6
Limestone - crushing and washing of
limestone powder for cement production NC_2 2.41 14.9 7.4
SlVk 2.5 11.7 5.5
Energy
IGM 2.57 13.3 11.8
Electricity - Electricity required for
48 K-1 2.46 43.1 8.2
blending of cementitious material
kWh/tonne K-3 2.48 27.2 9.6
cement K-5 2.38 32.8 6.3
[12] ZOR 2.52 41.1 10.8
Transport D-2 2.58 25.3 7.7
Emissions associated with
transportation of raw materials to cement The XRD quantification showed the clays from this
plant Ecoinvent area consist mostly of quartz, muscovite and a
Clay - Transported 200 km by truck database combination of other clay minerals such as kaolinite,
Limestone - Transported 300 km by illite and in some cases zeolite. Other impurities can be
truck found and the amorphous content of raw clays varies

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from 1 to even 47% (TOP_1). Interestingly, the strength. The life cycle assessment clearly shows a
samples containing higher amount of kaolinite have reduction of all impact categories when comparing
also a higher amount of these smaller particles. Density CEM I and the LCC mix.
of all particles was in the range from 2,1 to 2,6 g/cm3.
The pozzolanic reactivity test (R3) corelates with
the kaolinite content of the samples, pointing out the
differences between low and medium kaolinite clays.
Fig. 5 presents the results of this study, where samples
K1 and ZOR clearly show the highest reactivity with a
heat release of almost 400 J/g of SCM after 7 days
which corresponds to the higher kaolinite content.
Medium range clay of this study, D-5, shows medium
reactivity while the rest of the clays result with a heat
release between 150 and 250 J/g of SCM.
The relative compressive strength results are shown
in Error! Reference source not found. showing 2-
day, 7-day and 28-day compressive strength compared Fig. 7. LCA of CEM I and LCC cement
to the OPC reference. All mixtures show pozzolanic
properties when compared to the “inert” quartz mix. The highest reduction of environmental impact is
Mixes containing clays with a higher kaolinite content related to the Global warming potential (GWP) where
show a faster strength development with the highest calcined clay and limestone combination shows a
relative strength after 7 days. Surprisingly, the highest decrease of almost 40%. The smallest reduction can be
relative strength after 28 days is obtained with the clay seen in the abiotic depletion category which is affected
MAR, a middle range kaolinitic clay, followed by the mainly by the extraction of natural resources such as
two clays with the highest kaolin content – ZOR and clay.
K1. It is observed that the clays with the higher
kaolinite content obtain a higher development of early

120%

2 day strength 7 day strength 28 day strength

100%
Relative compressive strength (%)

80%

60%

40%

20%

0%

Fig. 8. Compressive strength of mortars containing calcined clay sample

4. Conclusion  There are significant differences in the

composition of clays, mainly in the amounts
This study focuses on the characterisation of different of alumina, silica and iron oxides, and the
regionally available clay for the use as suitable SCMs. kaolinite content.
The correlation between composition of the samples to
 Clay samples with the highest amount of
the reactivity and compressive strength provides a better
kaolinite (around 40%) show smaller
understanding of the material and the feasibility of their
amount of iron oxides and a higher amount
usage. The key findings of the study are:

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MATEC Web of Conferences 364, 05014 (2022)
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of smaller particles (<1 µm) after the same
treatment as others.
 All clays show pozzolanic reactivity when
compared to the inert quartz powder mix,
outperforming in compressive strength of
mortars test.
 Clays with higher amount of kaolinite
exhibit higher reactivity within the R3 test
which correlates to the fastest contribution
to early strength (2- and 7-day strength).
 One clay sample (MAR) reached the
compressive strength of OPC after 28 days
even though the kaolinite content of 17%
and the R3 test do not support this result. It
could be that the higher illite content of this
clay also contributes to the pozzolanic
reaction after calcination at 850°C [14].
 The LCA study showed a significant
reduction of environmental impact when
implementing 50% of cement replacement
with a combination of limestone calcined
clay cement, lowering the GWP by 40% and
all other indicators by more that 30%.
Exception is the abiotic depletion potential
which has the slightest reduction due to clay
excavation.
Further studies should be conducted to investigate
which other mechanisms play a role in the compressive
strength development of low-grade kaolinite clays. There
is also a need to understand the contribution of the most
viable calcined clays from this study to the formulation
of hydration products. This should be expanded
eventually to assess the durability benefits of such clay
in concrete mixtures.
The presented research is a part of a scientific project
“Advanced low CO2 cementitious materials”, ACT (grant no.
IZHRZO 180590/1), financed within the Croatian–Swiss
Research Program of the Croatian Science Foundation and the
Swiss National Science Foundation with funds obtained from
the Swiss-Croatian Cooperation Program. The first two authors
also acknowledge the support of the project “Alternative
binders for concrete: understanding microstructure to predict
durability”, ABC (grant no. HRZZ-UIP-2017-05-4767),
financed by Croatian Science Foundation.
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