Journal of Cleaner Production 183 (2018) 858e868

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Journal of Cleaner Production

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Effects of marble powder on the properties of the air-cured blended

cement paste
_
Nadhir Toubal Seghir a, Mekki Mellas a, Łukasz Sadowski b, *, Andrzej Zak c

a
Civil Engineering Research Laboratory, Biskra University, 07000, Biskra, Algeria
b
Faculty of Civil Engineering, Wroclaw University of Science and Technology, Wybrzeze Wyspianskiego 27, 50-370, Wroclaw, Poland
c
Faculty of Mechanical Engineering, Wroclaw University of Science and Technology, Wybrzeze Wyspianskiego 27, 50-370, Wroclaw, Poland

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

Article history: The objective of the research is to investigate the effect of the partial replacement of ordinary Portland
Received 7 November 2017 cement (PC) with waste marble powder (MP) on the physical and mechanical properties of air-cured
Received in revised form blended cement paste at the temperature of 22 ± 2
C and relative humidity about 20%. For this pur-
25 January 2018
pose, the MP was added to the cement paste to replace up to 15% of the cement's weight. Waste MP was
Accepted 31 January 2018
Available online 19 February 2018
extracted as the byproduct from the production of marble in an aggregate quarry in Algeria. The most
relevant physical and chemical properties of ordinary PC and MP were determined. The standard con-
sistency, setting time, apparent density, compressive strength and porosity were studied using the
Keywords:
Marble powder
methanol exchange method at 3, 7, 28 and 65 days. The results of this study indicate that the partial
Cement paste replacement of ordinary PC with MP affects the physical and mechanical properties of air-cured blended
Cleaner production cement paste. Finally, detailed microstructural analysis using scanning electron microscopy was per-
Compressive strength formed to confirm the obtained macroscopic properties.
Porosity © 2018 Elsevier Ltd. All rights reserved.
Scanning electron microscopy

1. Introduction treated as industrial waste. It is normally dumped in or near the

Marble is a metamorphic rock derived from pure limestone
(Ulubeyli and Artir, 2015). The purity of marble stone is responsible
for its color and appearance. It is white, what according to Chavhan
and Bhole (2014) it may indicate that limestone is composed solely of
calcite (100% CaCO3). The application of marble in civil engineering
and construction has recently increased (Aruntaş et al., 2010;
Buyuksagis et al., 2017; Rana et al., 2015). It is mainly due to its
use in floors, cladding, decoration, sculptures, etc. During its
extraction and production in an aggregate quarry, marble powder
(MP) is derived as an industrial byproduct. The presence of this
byproduct causes a serious environmental problem (Arel, 2016;
Galin ska and Czarnecki, 2017; Ergün, 2011; Munir et al., 2018;
Zeyad et al., 2017). It was reported by Hebhoub et al. (2011) that
around 70% of this mineral gets wasted in the stages of mining,
processing and polishing. It is even estimated that most of the rock
extracted in the Skikda region in the northeast of Algeria is also
quarry site and consequently creates an unacceptable environmental
impact. Sustainable destinations for these wastes need to be created.
It is necessary in order to eliminate this impact and to improve its
economic value. Mining byproducts are mostly non-biodegradable
and negatively affect the natural environment. Therefore, the utili-
zation of these wastes has become a priority problem from a sus-
tainable development point of view (Velay-Lizancos et al., 2017). As
pointed out by Santoro and Kripka (2017) contributions should al-
ways be taken into account at all of the life cycle phases of the uti-
lized waste. MP is normally not recycled in other branches of the
engineering industry. However, to assess the usability of this in-
dustrial waste in air-cured blended cement paste, all quality pa-
rameters need to be satisfied. The partial replacement of cement by
various industrial wastes and unprocessed micro-fillers can make
the air-cured blended cements cost effective (Agarwal and Gulati,
2006). Finally, the performance of air-cured blended cement paste
produced with such waste has to be defined.

2. Research significance
* Corresponding author.
E-mail addresses: tsnadhir@gmail.com (N. Toubal Seghir), m_mellas@yahoo.fr
(M. Mellas), lukasz.sadowski@pwr.edu.pl (Ł. Sadowski), andrzej.zak@pwr.edu.pl To highlight the significance of the study, Table 1 presents the
_
(A. Zak). most relevant recent studies related to the utilization of MP as a

https://doi.org/10.1016/j.jclepro.2018.01.267
0959-6526/© 2018 Elsevier Ltd. All rights reserved.
 N. Toubal Seghir et al. / Journal of Cleaner Production 183 (2018) 858e868 859

These curing conditions were optimum from the point of view of

Nomenclature and symbols the acceleration of the hydration rate of cementitious materials
made with MP (Arel, 2016; Binici et al., 2008; Munir et al., 2017). It
PC Portland cement has an important binding property due to the reaction between the
MP Marble powder calcite (CaCO3) and Tricalcium aluminate (C3A), which forms cal-
WMP Waste marble powder cium carboaluminates (Ulubeyli and Artir, 2015; Ergün, 2011; Arel,
WMD Waste marble dust 2016). In turn, as reported by Mashaly et al. (2016) the calcium
MS Marble sludge carboaluminates increase the total volume of the hydration prod-
WMS Waste marble slurry ucts and decrease the porosity. However, the cementitious mate-
SCC Self-compacting concrete rials on real-world construction sites are being stored mainly in air
SCM Self-compacting mortar conditions. According to the data presented in Table 1, there is no
SG Specific gravity () study related to the properties of the air-cured blended cementi-
Yad Apparent density (g/cm3) tious materials.
md Mass of dry cubes (g) Based on the performed literature review, there has only been
Vt Total volume of cubes (cm3) one study related to the cement paste level (Mashaly et al., 2016).
pm Porosity based on methanol exchange (%) However, it was performed with very fine powder (Blaine fineness
Vm Volume occupied by methanol in the samples of 6700 cm2/g). Also the specimens were cured in water and tested
(cm3) up to 28 days after concreting. Finally, the incorporation of MP into
Vt Total volume of samples (cm3) concrete and blended cements have a significant environmental
w Weight of methanol in the samples (g) and economical origin (Alyamaç and Aydin, 2015).
Ym Density of methanol (g/cm3) To the best of our knowledge, there is no study related to the
fcd Compressive strength (MPa) effect of the partial replacement of ordinary Portland cement (PC)
Cv Coefficient of variation (%) with waste MP on the physical and mechanical properties of air-
ps Porosity based on SEM analysis (%) cured blended cement paste. Although many important studies
have been published, several gaps in information remain, especially
regarding the properties of air-cured blended cement paste. To fill
this knowledge gap, this research will study the effect of the partial
cement replacement in cementitious materials. Thus, the related replacement of ordinary PC with waste MP on the physical and
research was reviewed to allow a better understanding of the mechanical properties of air-cured blended cement paste.
properties and performance of the air-cured blended cement pastes
to be produced.
The studies presented in Table 1 were performed mainly on 3. Materials and methods
mortar or concrete. Moreover, all the studies presented in Table 1
were performed on specimens that were cured in water. It can be 3.1. Materials treatment and the preparation of samples
seen from Table 1 that the Blaine fineness of used marble powders
differ from 1500 cm2/g to 12000 cm2/g. It depends on the available Portland cement CEM I 42.5 R, supplied by Biskria ciment
waste from the aggregate quarry and the treatment method. (http://www.biskriaciment-dz.com/Nos-Produits.aspx), and tap
Moreover, most studies show that the application of MP im- water were used in the study. The MP was obtained from the
proves the physical and mechanical properties of mortar and con- aggregate production of marble stone in the CHATT/Fil-Fila quarry
crete when cured in water conditions, both at early and late ages. of the Skikda region in the northeast of Algeria (https://www.
enamarbre.dz). To obtain a fineness of MP in the PC fineness

Table 1
Selected studies related to marble powder used as a cement replacement in cementitious materials.

Authors and reference Marble type and specific Blaine fineness Selected results
gravity (SG) (cm2/g)

Aruntaş et al., 2010
Ergün, 2011
Corinaldesi et al., 2010
Vardhan et al., 2015
Mashaly et al., 2016
Singh et al., 2017
Chaid et al., 2015
Talah et al., 2015
Boukhelkhal et al., 2016
Mohamadien, 2012
Aliabdo et al., 2014
Ashish et al., 2016
Alyamac et al., 2017
Belaidi et al., 2012, 2016
Bensalem et al., 2017
Güneyisi et al., 2009
Gesoglu et al., 2012
Sardinha et al., 2016
Khodabakhshian et al., 2018
WMD with SG ¼ 2.60 3097 Improved the fcd of mortar WMD content < 10%.
WMP with SG ¼ 2.68 5960 Improved the mechanical properties of concrete with MP content <5%.
MP with SG ¼ 2.55 1500 Decreased the fcd of mortar with MP content of 10%
MP with SG ¼ 2.60 3290 Improved the workability and fcd of mortar with MP content <10%.
MS with SG ¼ 2.67 6700 Improved the properties of cement paste and concrete with MP content <20%
WMS with SG ¼ 2.67 3500 Improved the fcd of mortar with MP content of 10%. The mechanical properties of
concrete with MP content <10%.
MP 12000 Improved the physical and chemical properties and durability of concrete with MP
content of 10%.
MP 11500 Improved the durability without decreasing the fcd of concrete with MP content <15%.
MP with SG ¼ 2.70 3600 Improved the fresh properties and decreased the fcd of SCC.
MP with SG ¼ 2.50 e Improved the fcd of mortar with MP content of 15%.
WMD with SG ¼ 2.50 3996 Improved the fcd of mortar and concrete with MP content <10% and of 15%, respectively.
WMP with SG ¼ 2.21 e Improved the flexular strength of concrete with MP content <10%
MP with SG ¼ 2.71 e Improved the fresh properties of SCC.
MP SG ¼ 2.70 3500 Improved the rheological properties of the SCM and SCC and decreased the fcd of SCC.
MP with SG ¼ 2.76 4200 Improved the mechanical properties of SCC.
MP with SG ¼ 2.81 e Improved the fresh properties of SCM and decreased the hardened properties.
MP with SG ¼ 2.71 5190 Improved the viscosity of SCC and decreased the mechanical properties with
MP content <20%.
MS with SG ¼ 2.73 2150 Decreased the density and the fcd of concrete with MS content <20%,
WMP with SG ¼ 2.50 e Decreased the fcd of concrete with WMP content <20%.
860 N. Toubal Seghir et al. / Journal of Cleaner Production 183 (2018) 858e868
Table 2
Mixture proportions of cement paste.
MP content (%) PC (%) w/b
0 100 0.40
5 95
10 90
15 85
range, it was necessary to first grind it using the Planetary Mills
classic line grinder from the brand “Fritsch”.
The specific gravity was determined using the pycnometer
method. The bulk density was determined using apparatus with a
sieve funnel and tripod, a unit weight measure of 1-L capacity, a
spatula, a straight edge and an aluminum scoop. Blaine apparatus
was used to determine the fineness of the material.
The mineralogical composition was determined using a D8
ADVANCE - X-ray Powder Diffractometer and calculated using the
Bogue equation (Hewlett, 2003). The chemical composition was
obtained by Zetium - X-ray Fluorescence Spectrometry.
In order to evaluate the effect of MP as a partial replacement of
PC on the properties of air-cured blended cement paste, the water-
to-binder ratio was kept constant at 0.4 in all mixes for testing the
hardened properties of cement pastes. The replacement of PC was
5%, 10% and 15% by cement weight and tap water was used. The
mixture proportions are presented in Table 2.
To determine the apparent density and compressive strength,
six cubes (50 mm) were prepared. In order to determine the
porosity using the methanol exchange method, six prisms
(40  40  160 mm) were also prepared. These specimens were
compacted using a vibrating table then kept for 24 h in moulds.
After demoulding, all specimens were stored in a laboratory at an
ambient air temperature of 22 ± 2
C for 3, 7, 28 and 65 days.
3.2. Experimental procedure
To determine the amount of required water and to evaluate the
initial-final setting times, Vicat needle apparatus was used ac-
cording to the requirements of EN 196-3 (EN 196-3, 2005). The test
was performed at an ambient temperature of 22 ± 2
C.
According to Kirgiz (2016), the apparent density (gad ) of the
cubes (50 mm) was measured by dividing the mass of dry cubes
(md) by the total volume of cubes (Vt):
md
gad ¼
Vt
Determination of the porosity (pm) value was performed using
the methanol exchange method. This method enables all water
existing inside the samples to be replaced by methanol.
The Pm (Eq (2)) was measured on samples with a thickness
of 8 ± 1 mm, which were extracted from mid-prisms
(40  40  160 mm). These samples were placed inside the meth-
anol until reaching a constant weight at between 3 and 14 days.
They were then dried over silica gel for 24 h at a temperature of
20
C (Ash et al., 1993; Mellas et al., 2003; Parrott, 1981).
Vm
pm ¼
Vt
where:
pm: porosity based on the methanol exchange method (%),
Vm: volume occupied by methanol in the samples (g),
Vt: total volume of samples (cm3).
The volume of methanol was determined using the following
formula:
w
Vm ¼ (3)
gm
where:
w: weight of methanol in the samples (g),
Vm: volume occupied by methanol in the samples (g),
Ym: density of methanol (0.79 g/cm3).
After determining the values of apparent density, the machine
Digimax plus 70-C0019/B” with a maximum capacity of 1000 KN
was used to determine the compressive strength (fcd).
Scanning electron microscopy (SEM) analysis was performed on a
sample of air-cured blended cement paste made with and without MP
after 28 days of being stored in air in order to see the change in
microstructure due to the incorporation of MP as a cement replace-
ment. The scanning electron microscope used for the observations
was a JEOL JSM-6610A, equipped with a tungsten hairpin filament. To
observe the microstructure of the material, the compositional mode
of the backscattered electron (BSE) detector was used with an accel-
eration voltage of 20 kV, a 40 nA beam current and a 10 mm working
distance. The blended cement paste samples for the microscopic
research were cold-mounted in an epoxy resin. Then they were
grinded and polished with 1 mm diamond paste. In order to obtain
electrical conductivity and to prevent electrical charging of the
specimen, the cleaned surface of the sample was covered with a
conductive path made of copper and the sample was then carbon
coated. A conductive layer with a thickness of 30 nm was applied in a
vacuum of 1,3 10 -4 Pa (10 -6 Torr) with the use of the thermal evap-
oration method and by using sharpened graphite rods.
4. Results and discussions
4.1. Marble powder (MP) and portland cement (PC) properties
The physical properties, chemical and mineralogical composi-
tions of PC and the MP used in the experimental study are given in
Table 3; the X-ray pattern of these materials is presented in Fig. 1.
As seen in Table 2, the results of X-ray fluorescence (XRF) indicate
that the chemical composition ratios of MP differ significantly from
those of PC. The major component of PC and MP is CaO, their pro-
portion an approximately 63% and 57% respectively. MP has very small
amounts of SiO2, Fe2O3 and Al2O3, with higher loss on ignition
compared to those of PC. Similar results were obtained by Hamza et al.
(2011), which indicate that calcium oxide is the major component of
MP with a proportion higher than 49% and small amounts of SiO2
(1) (<5%), MgO (<3%), and Fe2O3 (<2%) with loss on ignition of around
40%. On the other hand, MP and PC have a similar bulk density and the
Blaine fineness of both materials is in the same range.
The particle size distributions of PC and MP were performed
using a Malvern Mastersizer 2000 analyzer (liquid:Hydro,
2000MU). The results are presented in Fig. 2. The MP showed a
Blaine fineness value of about 3869.46 cm2/g. The single MP par-
ticles were less than 80 mm, 30 mm and 5 mm, which represents
about 90%, 50% and 10% of the total material volume, respectively.
In turn, the PC showed a Blaine fineness value of about
3571.78 cm2/g with particles less than 45 mm, 17 mm and 3 mm,
which represents about 90%, 50% and 10% of the total material
(2) volume, respectively.
4.2. X-ray diffraction analysis
X-ray diffraction (XRD) was used to identify the main mineral-
ogical components of PC and MP. As shown in Fig. 1-a, the XRD
spectrum of PC indicates the presence of four minerals, namely:
C3S, bC2S, C3A, and C4AF, as well as gypsum (CaSO4.2H2O).
 N. Toubal Seghir et al. / Journal of Cleaner Production 183 (2018) 858e868 861

Table 3 4.3. Properties of fresh cement paste

Chemical, mineralogical and physical properties of PC and MP.

PC MP The selected properties of the fresh cement and binder pastes

Oxide content (%)
are presented in Table 4. According to this table, it can be seen that
Silicon dioxide (SiO2) 20.83 0.05 the MP did not have a significant effect on the consistency and
Aluminum oxide (Al2O3) 4.13 0.05 setting times of the fresh cement paste. It is because the fineness
Iron oxide (Fe2O3) 5.58 0.02 of MP (3869.46 cm2/g) is similar to that of PC (3571.78 cm2/g). This
Calcium oxide (CaO) 62.91 56.94
is similar to those in the literature of the subject (Aliabdo et al.,
Magnesium oxide (MgO) 1.42 0.92
Sulfur trioxide (SO3) 2.30 0.32 2014).
Potassium oxide (K2O) 0.38 0.009 The amount of water required for normal consistency was found
Chlorine (Cl) 0.028 0.001 in the range from 25% to 35%, which complies with ASTM C 187-11e1
Loss on ignition (%) 2.04 41.63
(ASTM C 187-11e1, 1994). According to the ASTM C 150 - 04 (ASTM C
Mineralogical composition using the Bogue equation
Tricalcium silicate (C3S) 62.03 e
150 - 04, 2004) limits, the initial setting time should be greater than
Dicalcium silicate (C2S) 13 e 2700 s and the final setting time should not exceed 22500 s. The
Tricalcium aluminate (C3A) 1.5 e obtained results were found to be in this range (Table 4).
Tetracalcium aluminoferrite (C4AF) 16.98 e
Physical properties
Specific gravity (g/cm3) 3.15 2.74 4.4. Properties of hardened cement paste
Bulk density (g/cm3) 0.98 0.98
Blaine fineness (cm2/g) 3571.78 3869.46
Fig. 3 shows the changes of the Yad when using MP as a
partial replacement of PC at a content of 0%, 5%, 10% and 15% at
Regarding the MP, the XRD spectrum (Fig. 1-b) showed that different ages (3, 7, 28 and 65 days). It can be seen from Fig. 3
calcite, in addition to the presence of small amounts of dolomite that the Yad slightly decreases with the increase of MP content
(CaCO3.MgCO3), is the main crystalline mineral (CaCO3) Similar when compared to the control air-cured blended cement paste.
results were proved by other relevant studies (Ercikdi et al., 2015; This can be due to the presence of ultrafine particles, which
Ergün, 2011; Sadek et al., 2016). contributes to a decrease in the Yad of the matrix. Generally,
the change in the Yad of the samples was almost imperceptible

Fig. 1. X-ray diffraction (XRD) spectrum of PC (a) and MP (b).

MP a er grinding PC WMP
MP a er grinding PC WMP
100.0 10.0
90.0 9.0
80.0 8.0
Cumula ve (%)

70.0 7.0
Volume (%)

60.0 6.0
50.0 5.0
40.0 4.0
30.0 3.0
20.0 2.0
10.0 1.0
0.0 0.0
0.1 1 10 100 1000
Par cle Size (μm)
Fig. 2. Particle Size Distribution (PSD) of used materials.
862 N. Toubal Seghir et al. / Journal of Cleaner Production 183 (2018) 858e868

Table 4 (Rodrigues et al., 2015; Singh et al., 2017). In addition, the

Selected properties of fresh binder paste. specific gravity of the MP is lower than the specific gravity of
MP content (%) Normal Initial setting Final setting the cement (Gencel et al., 2012; Mashaly et al., 2016; Rodrigues
consistency (%) time (s) time (s) et al., 2015).
0 27.5 9300 ± 600.00 18000 ± 600.00 At all ages, the MP content from 5% to 15% decreases the Yad
(Cv ¼ 6.45%) (Cv ¼ 3.33%) from 1% to 2.80% when compared to the control air-cured blended
5 27.5 9300 ± 519.62 18000 ± 519.62 cement paste.
(Cv ¼ 5.59%) (Cv ¼ 2.89%)
The results of the compressive strength (fcd) of the cement paste
10 27.7 10500 ± 519.62 17400 ± 519.62
(Cv ¼ 4.95%) (Cv ¼ 3.45%) containing a MP content of 0%, 5%, 10% and 15% at different ages (3,
15 27.7 10500 ± 600.00 17400 ± 600.00 7, 28 and 65 days) are given in Fig. 4.
(Cv ¼ 5.71%) (Cv ¼ 6.90%)

*The values in parentheses are a coefficient of variation (cv).

2.01
1.986+0.003 At 3 days At 7 days
Cv=0.15%
1.99
1.976+0.001
1.966+0.006 At 28 days At 65 days
Cv=0.05%
Cv=0.31%
1.97
1.948+0.003 1.956+0.003
Cv=0.15% 1.944+0.003
Cv=0.15%
Cv=0.15%
1.95 1.930+0.003
(g/Cm3)

1.934+0.004 1.927+0.005 1.935+0.005 Cv=0.05%

Cv=0.21% Cv=0.26% Cv=0.26%
1.93 1.921+0.003
1.915+0.002 1.906+0.005 Cv=0.16%
Cv=0.10%
ad

Cv=0.26%
1.91 1.894+0.003
1.894+0.001 Cv=0.16%
Cv=0.05%
1.881+0.003
1.89 Cv=0.16%

1.87

1.85
0 5 10 15
MP content (%)
Fig. 3. Effect of the marble powder (MP) content on the apparent density (Yad) of cement paste at different curing ages.

60
At 3 days At 7 days
55
48.60+0.46 47.10+0.25 At 28 days At 65 days
Cv=0.13% Cv=0.53%
50 47.00+0.06 45.90+0.70 44.60+0.11
Cv=0.13% Cv=1.53% 43.50+0.29 Cv=0.25% 42.70+0.53
45 40.60+0.22 Cv=0.67% Cv=1.24%
40.10+0.14
Cv=0.54% Cv=0.35% 40.30+0.33
40
fcd (MPa)

36.20+0.33 Cv=0.82%
33.07+0.37 32.33+0.63 Cv=0.91% 33.40+0.22
35 Cv=1.12 % Cv=1.95% 30.67+0.80 Cv=0.66%
Cv=2.61% 28.27+0.32
30 Cv=1.13%

25
20
15
10
0 5 10 15
MP content (%)
Fig. 4. Effect of the marble powder (MP) content on the compressive strength (fcd) of cement paste at different ages.
 N. Toubal Seghir et al. / Journal of Cleaner Production 183 (2018) 858e868 863

32
At 3 days At 7 days
31
At 28 days At 65 days
30
28.73+0.01
29 27.95+0.01 Cv=0.03% 27.69+0.07
Cv=0.04%
Cv=0.25%
28 27.04+0.02 26.77+0.07
Cv=0.07% Cv=0.26% 25.35+0.02
27 26.37+0.02 25.28+0.03
Cv=0.08% Cv=0.12% Cv=0.08%
pm (%)

24.67+0.02 24.92+0.06
26 23.93+0.01 Cv=0.08% Cv=0.24%
23.53+0.01 Cv=0.04%
25 Cv=0.04%
24.22+1.24
23.75+1.71 Cv=5.12%
24 21.98+0.05 Cv=7.2%
Cv=0.23%
23
21.62+0.62
22 Cv=2.87%

21
20
19
0 5 10 15
MP content (%)
Fig. 5. Effect of the marble powder (MP) content on the porosity of cement paste at different ages.

As can be seen from Fig. 4, the fcd as a function of age (3, 7, 28 and 65
days) decreases subsequently with the increase of MP content in
the air-cured blended cement paste. The decrease in fcd was also
attributed with the decrease of Yad.
Compared to the control air-cured blended cement paste, the
increase of the MP content from 5% to 15% affects the accompa-
nied decrease of the fcd at 3 days from 2% to 15%, at 7 days from 1%
to 17%, at 28 days from 2% to 14%, and at 65 days from 3% to 12%.
This decrease may be due to the significant reduction of C3S and
C2S in the air-cured blended cement paste, which is mainly
responsible for compressive strength. This phenomenon is
commonly known as the dilution of pozzolanic reactions (Aliabdo
et al., 2014; Ergün, 2011; Heikal et al., 2000; Mashaly et al., 2016;
Meddah et al., 2014).
The test results of the porosity (pm) at different ages of the air-
cured blended cement paste containing MP are presented in
Fig. 5. The results show that the pm increases with the increase of
MP up to 15% at all ages. This may be explained by the decrease in
the volume of hydration products. This may be due to the reduction
of C3S and C2S in the cement paste (Aliabdo et al., 2014; Mashaly
et al., 2016). It can be seen that the water that was not absorbed
by the PC and MP evaporated. The loss of this part led to an
incomplete hydration process and an increase in the air void
content.
In comparison with the control specimen, the increase of MP
from 5% to 15% led to an increase in the pm from 2.54% to 8.95% at 3
days, 7.44%e17.68% at 7 days, 8.87%e15.33% at 28 days, and 9.95%e
15.32% at 65 days.
Fig. 6 shows the scanning electron microscopy (SEM) of the
air-cured blended cement paste containing MP as a replace-
ment at 28 days. Back-scattered Electrons (BSE) images show
that the structure of air-cured blended cement paste made
with MP from 0% to 15% is different. It is visible that the
control cement paste has a compact microstructure. It can also
be seen that the increase of MP led to an increase in the
percentage of voids and also in the percentage of calcium hy-
droxide (CH). This may be due to the decrease of the chemical
composition of PC, especially SiO2, when using MP as a cement
replacement.
The results of the percentage of hydrate products were deter-
mined by Energy-dispersive X-ray spectroscopy (EDX) (Fig. 7 and
Table 5). The results indicate that the increase of MP led to a
decrease of silicate hydrate (measured as Si) at all ratios of
replacement.
The replacement of cement with MP of up to 10% increases
the content of calcium hydrate (Ca) due to the presence of
calcite (CaCO3) in MP. On the other hand, the content of
aluminum hydrate (Al) and iron hydrate (Fe) decreases due to
the smaller content of aluminum oxide (Al2O3) and ferric oxide
(Fe2O3) in MP.
It can also be seen that the use of MP with a high replace-
ment ratio (such as 15%) led to a decrease in the amount of Ca.
This can be due to the increase of the amount of water required
for MP as a result of its absorption. Thus, the loss of some of the
water absorbed by MP led to a lower hydrate product in PC
(especially Ca) being obtained. The subsequent increase of the
percentage of Al and Fe hydrates may be due to the reaction of
tricalcium aluminate (C3A) with calcite (CaCO3). As mentioned
by Ulubeyli and Artir (2015), Ergün (2011) and Arel (2016), this
reaction led to the forming of calcium carbo-aluminates (CCA).
The CaCO3 then reacts with tetracalcium-aluminoferrite to form
calcium carbo-aluminoferrites (CCAF) (Ingram and Daugherty,
1991).
The percentage of calcium hydroxide (CH) and porosity were
determined on a higher magnification, as shown in Fig. 8. The
backscattered images and chemical mappings were treated by
864 N. Toubal Seghir et al. / Journal of Cleaner Production 183 (2018) 858e868

Fig. 6. Back-scattered Electrons (BSE) images (left) and Si EDX mapping (right) of cement paste with different MP contents (CH ¼ calcium hydroxide (shown in black circle); V ¼ air
voids (shown in red circle).

ImageJ software in order to determine the percentage of the area an increasing MP content. In addition, the size of the area of
of CH and porosity. The CH is shown in the images as black par- porosity also increased. The results of the percentage area of CH
ticles and the porosity is shown as red particles. From these im- and porosity are presented in the table that is integrated into
ages, it can be observed that the CH and porosity increased with Fig. 8.
 N. Toubal Seghir et al. / Journal of Cleaner Production 183 (2018) 858e868 865

Fig. 7. Energy-dispersive X-ray spectroscopy (EDX) of cement paste replacement with different MP contents obtained with a 20 kV accelerating voltage.

cement paste containing 5%, 10% and 15% of MP resulted in an in-

crease of the CH area by 0.340%, 8.214% and 3.210%, respectively. It
Table 5 can be seen that the CH area of air-cured blended cement paste
Hydrate products of hardened cement pastes.
containing 15% of MP decreases when compared to the air-cured
MP (%) 0 5 10 15 blended cement paste containing 10% of MP. This is confirmed by
Element (%) the results of EDX, which indicates that the content of Ca hydrate in
Oxygen (O) 49.77 51.26 50.64 51.56 the air-cured blended cement paste containing 15% of MP was
Calcium (Ca) 30.12 32.26 34.05 31.84 lower than that present in the air-cured blended cement paste
Silicon (Si) 10.78 9.22 8.99 8.75 containing 10% of MP.
Iron (Fe) 4.92 3.52 3.05 3.87
Aluminum (Al) 2.72 2.12 1.76 2.35
The increase of CH content and the decrease of silicate hydrate
Magnesium (Mg) 0.94 0.87 0.86 0.88 (Si) mean that the C-S-H was decreased, and therefore the increase
Sulfur (S) 0.75 0.75 0.66 0.75 of MP ratio led to a decrease of the C-S-H content. This decrease of
Total 100 100 100 100 C-S-H allowed for an increase of porosity.
Finally, the results of SEM analysis and EDX confirm the test
results of the porosity using the methanol exchange method and
also the compressive strength.
As seen in the table integrated into Fig. 8, the increase of The relationship between compressive strength and the
MP content from 0% to 15% led to an increase in porosity from apparent density, compressive strength (Eq (1)) and porosity
13.47% to 22.77%. In addition, the SEM analysis indicate that based on the methanol exchange method at all curing ages (Eq
the average size of air voids was increased from 9.01E-04 mm2 (2)), the compressive strength, porosity based on the methanol
to 1.83E-03 mm2. These results were confirmed by the results exchange method (Pm) (Eq (3)) and porosity based on SEM
of porosity (Pm), which was determined using the methanol analysis (Ps) (Eq4) at 28 days are presented in Figs. 9e11,
exchange method on the samples with a total area of respectively.
1600 mm2 and a thickness of 8 ± 1 mm. In addition, the average It can observe from these figures that the properties of air-
size of air voids was increased from 9.01E-04 mm2 to 1.83E- cured blended cement paste have a good relationship. In addi-
03 mm2, but the SEM analysis was done on samples have total tion, the trend in compressive strength is to increase with
area of 225 mm2. increasing of apparent density and with decreasing of porosity for
The results of porosity by SEM analysis show a good relationship all mixture.
with the results of porosity by methanol exchange method. How-
ever, the SEM analysis is more accurate due to give all necessary
5. Conclusions and perspectives
information on the percentage and the average size of air voids. On
the other hand, the content of CH increased from 0.203 to 8.214
The aim of this study was to evaluate the effect of the partial
with an increase of MP ratios.
replacement of cement with waste marble powder on the proper-
When compared to the control mix, the air-cured blended
ties of air-cured blended cement paste. From this study, the
866 N. Toubal Seghir et al. / Journal of Cleaner Production 183 (2018) 858e868

0 % MP 5 % MP

10 % MP 15 % MP

Fig. 8. Magnified SEM image of cement paste containing MP as a replacement - CH ¼ calcium hydroxide (shown in black particles); V ¼ voids (shown in red particles).

55

50

45
fcd = 0,0023e5,0392 ad
fcd (MPa)

R ² = 0.7841
40

35

30

25
1.85 1.87 1.89 1.91 1.93 1.95 1.97 1.99 2.01
ad (g/cm )
3

Fig. 9. The relationship between the apparent density and compressive strength of cement paste at all curing ages.
 N. Toubal Seghir et al. / Journal of Cleaner Production 183 (2018) 858e868 867

60 5. The porosity based on the methanol exchange method showed a

very good relationship with the porosity based on SEM analysis.
55

50
According to these results, it can be concluded that if the w/b
fcd = 262.94e-0.075Pm ratio increases by more than 0.4, or if the samples are cured in
R ² = 0.8497
fcd (MPa)

45 water, the results will show a decrease in compressive strength and

an improvement in porosity.
40 The general conclusion of this study is that the incorporation of
35
waste marble powder was beneficial. The properties of air-cured
blended cement paste with MP tended to decline for replacement
30 ratios of more than 10%. Acceptable results were obtained for a
replacement ratio of MP of up to 5%. In this case, no significant loss
25 of the compressive strength of air-cured blended cement paste was
20 22 24 26 28 30
observed.
Pm (%)
As pointed out by Czarnecki and Van Gemert (2017) recently
Fig. 10. The relationship between the compressive strength and porosity of cement construction have become dangerously detached from their
paste at all curing ages. ecological context. Thus, in this configuration the waste products

55
Porosity based on methanol exchange method
53
Porosity based on SEM analysis
51
49 fcd = 118.64e-0.041Pm
R² = 0.7751
47
fcd (MPa)

45
43 fcd = 59.929e-0.017Ps
41 R² = 0.8896

39
37
35
10 12 14 16 18 20 22 24 26 28 30
P (%)
Fig. 11. The relationship between the compressive strength and porosity of cement paste at 28 days.

following conclusions can be drawn:
1. The consistency and setting times of cement pastes are slightly
changed in a very low range with the use of MP as a cement
replacement, the initial setting time was changed from 9300 to
10500 s and the final setting time was changed from 17400 to
18000 s, this change can be neglected at the scale of rheological
characteristics of cement paste.
2. The compressive strength of air-cured blended cement paste
decreases by up to 14% at 28 days with the use of MP as a cement
replacement, due to the reduction of the apparent density of air-
cured blended cement paste, increase of the porosity of air-
cured blended cement paste and reduction of the C-S-H
products.
3. The porosity of air-cured blended cement paste increased by up
to 15% at 28 days with an increasing percentage of MP due to the
reduction of C3S and C2S in air-cured blended cement paste.
Additionally, some of the water required in the hydration pro-
cess was evaporated.
4. The SEM analysis and EDX indicated that the use of MP as a
cement replacement led to an increase in the CH content and a
decrease in the C-S-H content, which allowed for an increase of
the porosity area in the air-cured blended cement paste.
from the marble stone aggregate quarries in Algeria can be reused,
which allows to the reduction of waste and to obtain a sustainable
and economical cementitious materials. It allows for a reduction of
greenhouse gases emissions and also the saving of more natural
resources. Thus, air-cured blended cement with the addition of
marble powder can be certainly included in the sustainable and
environmentally friendly category.
Due to the low density of applied marble powder compared to
the density of cement in construction practice it may be econom-
ically sensible to utilize of marble powder for example in light-
weight cementitious materials production. Recent tries performed
using oil palm shell and rice husk ash were found to be successful
(Farahani et al., 2017). We may also suppose that the future
perspective for utilization of marble powder may be connected
with the possibility to reduce CO2 by accelerated mineral carbon-
ation. As reported recently by Kaliyavaradhan and Ling (2017) the
industrial wastes are popular for this purpose (e. g. steel slag, fly
ash, municipal incinerator ash, or cement kiln dust).
Acknowledgments
Part of this research was done during the author's first visit to
Wroclaw University of Science and Technology, Poland. The authors
868 N. Toubal Seghir et al. / Journal of Cleaner Production 183 (2018) 858e868
would like to especially acknowledge the support of the Electron
Microscopy Laboratory at Wroclaw University of Science and
Technology for all aspects and facilities that enabled the SEM
analysis to be performed.
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