Construction and Building Materials 81 (2015) 130–139

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Construction and Building Materials

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Hydration study of ternary blended cements containing ferronickel slag

and natural pozzolan
N. Lemonis a, P.E. Tsakiridis b,⇑, N.S. Katsiotis a, S. Antiohos c, D. Papageorgiou c, M.S. Katsiotis d,
M. Beazi-Katsioti a
a
National Technical University of Athens, School of Chemical Engineering, Laboratory of Analytical and Inorganic Chemistry, 9 Heroon Polytechniou St, 15773 Athens, Greece
b
National Technical University of Athens, School of Mining and Metallurgical Engineering, Laboratory of Physical Metallurgy, 9 Heroon Polytechniou St, 15780 Athens, Greece
c
Titan Cement Company S.A., Athens, Greece
d
Chemical Engineering Department, The Petroleum Institute, PO Box 2533, Abu Dhabi, United Arab Emirates

h i g h l i g h t s

 Ferronickel slag and volcanic pumice pozzolanic additions to Portland cement.

 Physical and mechanical properties of binary and ternary mixes evaluation.
 Hydration degree and pozzolanic reaction confirmed by XRD, TG–DTG and SEM.
 All mixtures satisfied the requirements for the strength class 42.5 as per standard EN 197-1.

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

Article history: The present investigation focuses on the hydration evolution of ternary blended cements composed by
Received 25 October 2014 natural pozzolan (NP) and ferronickel slag (FNS), which is produced during the pyrometallurgical treat-
Received in revised form 29 January 2015 ment of laterites for the production of ferronickel. The slag and pozzolan were grounded to a specific sur-
Accepted 18 February 2015
face area of 4000 cm2/g and twelve different cement mixtures were produced containing up to 20%
Available online 2 March 2015
Portland cement replacement with the above-mentioned cementitious materials. The produced blended
cements were tested by determining their initial and final setting times, standard consistency, flow of
Keywords:
normal mortar, soundness and compressive strength at 2, 7, 28, 56 and 90 days. X-ray diffraction and
Ferronickel slag
Pozzolan
TG/DTG analyses were used for the determination of the hydration products, whereas the microstructure
Blended cements of the hardened cement pastes and their morphological characteristics were examined by scanning elec-
Hydration tron microscopy. According to the results, the ferronickel slag could be readily utilized together with nat-
ural pozzolan as substitutes for cement, presenting significant environmental benefits in waste
management practice.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction production process, whereas the average CO2 emissions ranges

Despite the notable progress during the last decades, cement
sector not only has been one of the most energy intensive indus-
tries in the world, but accounts for around 5% of the global green-
house gas emissions, because of the burning of fossil fuels during
sintering process in rotary kiln and due to the limestone decompo-
sition, the main constituent of the raw meal. The production of one
tone of cement requires 60–130 kg of fuel oil or its equivalent and
about 105 kWh of electricity, depending on the cement type and
⇑ Corresponding author. Tel.: +30 210 7722181; fax: +30 210 7722218.
E-mail address: ptsakiri@central.ntua.gr (P.E. Tsakiridis).
from 0.60 to 1 tons of CO2 per cement tone [1,2].
Although the production process is still very energy consuming,
cement is the most widely used construction material today. Due
to the regulations, policies and environmental sustainability, the
need for energy consumption decrease, as well as for CO2 emission
lowering, implied the pure cement replacement from supplemen-
tary cementitious materials (SCM), which are used in order to pro-
duce what is generally called as ‘‘blended cements’’. The most
common SCM are natural pozzolans, generally derived from vol-
canic origins and artificial pozzolans, which are mainly industrial
byproducts/wastes, such as fly ash, different type of metallurgical
slags and silica fume. Blending Portland cement with pozzolanic
admixtures is an effective way to improve workability, strength

http://dx.doi.org/10.1016/j.conbuildmat.2015.02.046
0950-0618/Ó 2015 Elsevier Ltd. All rights reserved.
 N. Lemonis et al. / Construction and Building Materials 81 (2015) 130–139 131

100

Cumulative Number of Particles (wt%) 80

FNS

NP

60

40

20

0
100 1000 10000

Particle Diameter (μm)

Fig. 1. Particle size distribution of FNS and NP used.

Table 1
Chemical analysis and physical characteristics of cement and slag used. and durability (lower permeability, resistance to chlorides and sul-
Oxides Chemical analysis (wt%)
fates, mitigation of alkali silica reaction) [2–5]. An additional ben-
efit of the above approach is that many pozzolanic materials used
CEM I52.5 FNS NP
for blending today would be otherwise stockpiled or disposed in
SiO2 21.25 41.18 72.14 landfills, presenting environmental hazards such as dust con-
Al2O3 3.77 5.98 12.81
tamination or leaching of heavy metals in groundwater. As a result,
Fe2O3 4.27 40.02 1.25
CaO 64.35 4.12 0.84 this reuse and recycling approach in blended cement production
MgO 1.25 7.79 0.19 contributes to the solution of major environmental problems. The
K2O 0.44 0.37 4.09 present paper focuses on the properties and hydration of ternary
Na2O 0.12 0.09 2.38 blended cements, produced by pure Portland cement and two
SO3 2.40 0.64 0.02
MnO 0.15 0.52 0.05
SCM; ferronickel slag and natural pozzolan.
TiO2 0.23 0.12 0.13 Greece is rich in natural pozzolans (NPs), materials originated
NiO 0.05 0.13 – from volcanic eruption. The pumice used in this study is coming
Cr2O3 0.13 2.75 0.04 from Gyali, a small volcano islet in the Dodecanese islands, which
Free CaO 0.15 – –
belongs to the southern Aegean volcanic arc. The south-western
LOI 1.25 3.44 5.04
part of the islet is formed by pumice whereas the north-eastern
Physical characteristics
part by obsidian domes and rhyolitic lava flows [6,7]. The pumice
Specific surface (cm2/g) 3870 3985 3940
Specific gravity (g/cm3) 3.14 3.18 2.37 stone quarry is operated using the method of vertical benches
and the quarry’s production capacity in the form of natural pumice
is up to 800.000 t/y. It is characterized by a high content of vitreous
components and its high pozzolanic reactivity is mainly attributed
to the high content of active SiO2; it can react with calcium hydrox-
Table 2
ide released during the hydration of cement to produce C–S–H gels.
Composition and characteristics of cement mixtures.
Studies of the influence of the pumice blended cements showed
Code CEM I52.5 FNS NP Specific surface area Specific gravity that in percentages up to 20% results in positive strength develop-
(wt%) (wt%) (wt%) (cm2/g) (g/cm3)
ment [8–10].
CRef 100 – – 3870 3.14 On the other hand, the ferronickel slag (FNS) is a byproduct
CS5 95 5 – 3875 3.14
obtained from smelting of laterite ore in an electric arc furnace
CS10 90 10 – 3890 3.14
CS15 85 15 – 3905 3.15 at a high temperature with the presence of a reducing agent, for
CS20 80 20 – 3925 3.15 the production of ferronickel alloy [11,12]. The FNS from the elec-
CP5 95 – 5 3880 3.10 tro-reduction furnace is produced at a rate of approximately
CP10 90 – 10 3885 3.07 2000 kt/y and for every tone of FeNi alloy the amount of FNS pro-
CP15 85 – 15 3895 3.03
CP20 80 – 20 3900 2.99
duced is estimated at 4 tones [11,13]. Currently, FNS is granulated
CSP5 95 2.5 2.5 3870 3.11 through sudden cooling in sea water, leading to an amorphous
CSP10 90 5 5 3880 3.10 material, which, due to its properties it has been classified as
CSP15 85 7.5 7.5 3890 3.08 non-hazardous waste, according to the European Catalogue for
CSP20 80 10 10 3895 3.06
Hazardous Wastes [14].
132 N. Lemonis et al. / Construction and Building Materials 81 (2015) 130–139

600
1. C3S - Alite
2. C2S - Belite
3. C3A - Calcium Aluminate
1,2
4. C4AF - Ferrite
5. CaOf - Free Lime
6. MgO - Periclase
7. CaSO4 2H2O - Gypsum
8. [(Fe2+,Mg)(Fe3+,Al,Cr)2O4 - Spinel
9. SiO2 - Quartz 9 1,2
10. (Ca,Na)(Si,Al)4O8 - Anorthite

10,11
400 11. KAlSi3O8 - Orthoclase 1,2
Arbitrary Units (a.u.)

NP
1

8
200 FNS 8
1,2

8
3
4
7
CEM I52.5 1 1
4 1,2 2
1 1 2
7 2 6 1,2
7 4 1 2 5

0
5 10 15 20 25 30 35 40 45

2θ degree
Fig. 2. X-ray diffraction analysis of cement and slag used.

Me
Sp
Me

Me
Mgn Gl
Gl

Sp Sp

Gl
Gl

Ol
Me
Sp Sp Ol

Fig. 3. Backscattered electron micrographs of the as received FeNi slag polished sections. Fine to coarse-sized euhedral crystals of spinel (Sp) and pure magnetite (Mgn)
embedded in glassy matrix (Gl). Parallel growths of columnar elongated olivine-group crystals (Ol) in the amorphous glass (Gl) phase. Drop-like and vermicular metallic
particles composed of FeNi (Me).

In Greece, the slag from the ferronickel production had been legislation has limited its use in the building materials sector
used for a short period in the past (in the late 90s) as a mineral [15,16]. Today a small part of the produced FNS is used as a
admixture in the production of cement, but for the moment local sand-blasting material, as a raw material in cement clinker produc-
 N. Lemonis et al. / Construction and Building Materials 81 (2015) 130–139 133

tion, as an inert additive in high strength concrete, instead of lime- Table 3

stone aggregates in the light concrete for the construction of the Physical properties of blended cement pastes.

base of roads, or in producing anti-slippery pavement tiles [15]. Code Water Setting times Le Chatelier Flow of normal
However, the largest amount of the produced slag is temporary demand (min) soundness mortar
disposed in areas closed to the metallurgical plant. Although FNS (wt%) (mm) (%)
Initial Final
has been considered as non-hazardous, alternative ways for its CRef 27.8 145 185 0.5 97.5
exploitation should be introduced in order to reduce or eliminate CS5 27.6 150 195 0.7 100.2
cost of disposal and avoid potential soil and water contamination. CS10 27.0 160 200 0.8 104.7
Efforts have been carried out in laboratory and pilot-scale trials for CS15 26.5 170 215 1.3 107.9
CS20 26.1 175 220 1.4 110.5
the utilization of FNS in the production of high-alumina cement
CP5 27.5 160 195 1.2 100.5
[11], whereas recent researches have proof that FNS can be also CP10 26.9 170 205 1.5 105.5
used as raw material in synthesizing inorganic polymers (geopoly- CP15 26.3 175 210 1.9 108.7
mers), after alkali activation [17–19]. Although the above slag CP20 25.9 180 215 2.1 111.4
CSP5 27.6 155 200 0.8 100.3
could be considered as SCM, due to its high content in silicon oxide,
CSP10 27.1 165 205 1.2 105.1
the so far published literature has given little attention to its use in CSP15 26.6 175 210 1.5 108.2
producing composite Portland cement. In a previous work, the CSP20 26.1 180 220 1.8 110.9
properties and hydration of ferronickel slag blended cements con-
taining 5, 10, 15, and 20 wt% cement replacement were examined;
all cement mixtures satisfied the requirements for strength class
42.5 as per EN 197-1. In addition, the leachability behavior of the
produced blended cements was determined by the Toxicity Char- 2. Experimental

acteristic Leaching Procedure (TCLP) test and the tank diffusion
test for monolithic samples (NEN 7375). In all cases the concentra-
tions of leached heavy metals were found to be substantially below
the regulatory thresholds. [20].
In the present research study, the hydration of ternary blended
cements containing ferronickel slag and natural pozzolan was
examined. One reference cement and twelve mixtures containing
up to 20 wt% FNS and/or NP were prepared. Water demand, setting
times, soundness and compressive strength were measured. XRD,
TG/DTG and SEM were applied in order to study the combined
action of the Portland cement hydration and the pozzolanic reac-
tions of the added FNS and NP.
2.1. Raw materials
FNS, supplied from LARCO smelting plant located at Larymna and pumice, sup-
plied from LAVA Mining & Quarrying SA, were added to a CEM I52.5 Portland
cement. FNS presented a size fraction of 5 mm, whereas the corresponding of
NP was determined at 8 mm. Their particle size distribution was determined by
sieve analysis (Fig. 1).
Chemical analyses carried out with X-ray Fluorescence (Spectro-Xepos) and
Atomic Absorption Spectrophotometry (Perkin Elmer 4100) are shown in Table 1,
along with specimen physical characteristics. The mineralogical phases of FNS, NP
and CEM I52.5 used in this study were determined by XRD analysis on powders,
using a Bruker D8-Focus diffractometer with nickel-filtered CuKa radiation
(k = 1.5406 Å), at 40 kV and 40 mA. FNS and NP morphology and microstructure
was examined by a Jeol 6380LV Scanning Electron Microscopy (SEM).

Fel

Fel

Sil
Sil Fel
Feld

Fel
Hem

Fel
Sil Fel

Hem

Fig. 4. Backscattered electron micrographs of the as received NP polished sections. Oval and fibrous shaped pores with open channels dispersed in glassy matrix (Sil).
Feldspars (Fel), rich in alkalies, along spheroid hematite (Hem).
134 N. Lemonis et al. / Construction and Building Materials 81 (2015) 130–139

Table 4 Analysis (TGA) was carried out to evaluate hydration rate using a Mettler-Toledo
Compressive strengths of cements tested (MPa). TGA/SDTA 851 instrument. The exact boundaries for the temperature intervals were
defined from the derivative curve (DTG). Type R thermocouple (Pt-13% Rh/Pt) was
Code Days used for temperature measurements. Specimens were put in ceramic crucible and
2 7 28 56 90 heated from room temperature to 900 °C, at a constant rate of 10 °C/min, using
nitrogen as medium under static condition. Finally, morphological analysis and
CRef 24.1 39.2 54.2 60.5 63.5 observation of hydration products were performed with SEM at 20 kV using a Jeol
CS5 23.3 37.1 53.0 59.7 62.8 6380-LV equipped with an Oxford INCA Energy Dispersive Spectrometer (EDS).
CS10 21.1 33.0 50.5 58.1 60.1
CS15 19.0 29.9 48.7 56.9 59.1
CS20 17.2 27.8 47.1 55.8 58.2 3. Results and discussion
CP5 22.8 36.2 52.2 58.8 61.7
CP10 20.6 32.4 49.8 56.6 58.6
3.1. Raw materials
CP15 18.8 29.5 47.6 55.3 57.6
CP20 16.7 27.2 45.9 54.3 56.9
CSP5 23.1 36.8 52.8 59.6 62.1 The ferronickel high rate cooled slag appeared black–grey, opa-
CSP10 20.9 32.8 50.1 57.8 58.9 que and glassy. As mentioned above, the material is produced by
CSP15 18.9 29.7 48.3 55.8 58.3
cooling under a sea water shower, resulting in a size fraction of
CSP20 17.0 27.5 46.6 54.9 57.4
5 mm. Its particle size distribution is presented in Fig. 1. 90 wt%
of it exhibits a grain size smaller than 2 mm, whereas the 50 wt%
was below 0.9 mm. On the other hand, NP presented a size fraction
The reactive SiO2 of both FNS and NS was determined using the standard pro-
cedures specified in EN 196-2 [21]; defined as the fraction of silica which, after of 8 mm, with the 55 wt% of it being below 2 mm.
the treatment with hydrochloric acid, is soluble in boiling potassium hydroxide Chemical analysis is given in Table 1. In case of FNS, iron and
solution, in a 4 h extraction. The determination of their pozzolanicity was carried silicon were the main constituents and accounted for 81 wt% of
out according to the Hellenic National Standard 244/1980, which measures the abil- the slag mass. Other constituents such as Al2O3, CaO, MgO were
ity of slag to combine with lime due to pozzolanic reactions [16].
found in lower quantities. Regarding FNS pozzolanic activity, the
percentage of reactive silica was determined at 40.71 wt%, whereas
2.2. Blended cements its pozzolanicity was determined at 5.9 MPa (mortars of slag with
Ca(OH)2 and standard sand). NP is a pyroclastic acidic pumice,
Prior to the preparation of the blends with cement, the FNS (size fraction:
5 mm) and NP (size fraction: 8 mm) were ground, in a 1 kg laboratory ball mill characterized by its light coloring. Its chemical analysis revealed
using steel balls as grinding medium, to a specific surface area of 4000 cm2/g, that it is essentially a silicate of igneous origin, which has been
defined according to the Blaine air permeability method [22]. Following, the blend- formed by a process of explosive volcanism. It is principally com-
ed cements were produced by mixing both admixtures with the cement. The mixing posed of silicon, with minor amounts of aluminum iron and calci-
ratios, as well as the physical characteristics of the produced blended cements are
given in Table 2.
um. Although the NP reactive silica is higher than that of FNS and it
Standard consistency and setting times of cement pastes were determined using was determined at 55.14 wt%, its pozzolanicity is relatively lower
a Vicat apparatus according to the European Standard EN 196-3 [23]. The determi- and it was determined at 5.35 MPa.
nation of the normal mortar flow was carried out according to ASTM C1437 [24]. X-ray diffraction patterns of both FNS and NP (presented in
The soundness of the cement pastes were determined by the Le Chatelier method
Fig. 2) reveals their amorphous nature, as reflected by the presence
[23]. Compressive strength measurements were conducted at the ages of 2, 7, 28
and 90 days on mortar specimens (dimensions 40 mm  40 mm  160 mm), pre- of a diffuse wide band from the glassy phase, located approximately
pared and tested in accordance with European Standard EN 196-1 [25]. at 2-h 30° and is extended in the range of 20–40°. The spinel phase
To examine the hydration products, cement pastes were prepared by mixing [(Fe2+, Mg)(Fe3+, Al, Cr)2O4] was the only crystalline mineralogical
300 g of cement mixtures with 75 ml of water. Following, the pastes were left to phase that was detected in the slag. The formation of crystalline
cure in temperature controlled sealed vessels containing tap water (20 ± 2 °C). At
the ages of 2, 7, 28 and 90 days, the hydration was stopped by means of acetone
phases is a function of both the chemical composition of the melt
and ether extraction. The hydration products were mineralogically determined by and its cooling rate. In case of silica high content, the slag vitrifies
X-ray diffraction, using a Bruker D8-Focus diffractometer. Thermal Gravimetric (forms a glassy phase), when it is rapidly cooled. In case of NP, it

70

60
Compressive Strengths (MPa)

50
Reference

20 wt% FNS

20 wt% NP
40
20 wt% FNS+NP

30

20

10
0 10 20 30 40 50 60 70 80 90 100
Age (Days)

Fig. 5. Strength development of the blended cement with 20 wt% substitution.

 N. Lemonis et al. / Construction and Building Materials 81 (2015) 130–139 135

600
1. Ca(OH)2 7 . MgO
2. Ca 6Al2(SO4)3(OH)2 26H2O 8.Ca4Al2O6CO3 11H2O
3. CaCO3 9 . Ca 4Al2O6(CO3)0.5(OH) 11.5 H2O
4. C2S/C3S 10. Ca 2SiO4 xH2O
5. Ca 1.5SiO3.5 xH2O 11. Ca3(Si3O8(OH)2 )
500
6. Ca 2SiO4 0.35H2O

5,6
400
Arbitrary Units (a.u.)

3,4 1
1 1
2 1
90 days 11

4,6
1 5
10 8 2 2 1
9
300
2

28 days
4

200 4

7 days
4

100

2 days 2
4
7

0
5 10 15 20 25 30 35 40 45 50 55

2θ
Fig. 6. X-ray diffraction of CSP20 mixture with 10 wt% FNS and 10 wt% NP, hydrated at various ages.

600
1. Ca(OH)2 7 . MgO
2. Ca 6Al2(SO4)3(OH)2 26H2O 8.Ca4Al2O6CO3 11H2O
3. CaCO3 9 . Ca 4Al2O6(CO3)0.5(OH) 11.5 H2O
4. C2S/C3S 10. Ca2SiO4 xH2O
5. Ca 1.5SiO3.5 xH2O 11. Ca3(Si3O8(OH)2 )
500 6. Ca 2SiO4 0.35H2O

1
4,5

400
Arbitrary Units (a.u.)

3,4

2 1 4
CSP20 1
1 1
4,6

2 11 2
10 8 4 5 1
2 2

300

CP20
7

200

CS20
9
8

100

CRef

0
5 10 15 20 25 30 35 40 45 50 55

2θ
Fig. 7. X-ray diffraction of reference and blended cements with 20 wt% substitution, hydrated at 28 days.

is a pumice, which comprises an average of 85% volcanic glass along
with about 15% of feldspars, which were identified as anorthite and
orthoclase.
The above observations were also confirmed by SEM analysis.
Regarding FNS (Fig. 3), the glass phase appears colourless and is
chemically heterogeneous, as it consists mostly by silicon, iron,
aluminium and magnesium. It also exhibits elevated concentra-
tions of Ca. Within the isotropic glass, complex spinel phases
[(Fe2+, Mg)(Fe3+, Al, Cr)2O4] are the most abundant and some
magnesium silicate crystalline phases are less common. The metal
136 N. Lemonis et al. / Construction and Building Materials 81 (2015) 130–139
100
95
C-S-H
Mass Loss (%)
90
85
Ettringite
80
0 100 200 300
Temperature (oC)
Fig. 8. TG/DTG of reference and blended cements with 20 wt% substitution, hydrated at 28 days.
alloy is easy to distinguish as it exhibits higher reflectance when
compared to other minerals. Although the coarse alloy has been
recovered, the ferronickel slag still contains small amounts of
metallic particles with various complicated forms (drop-like, ver-
micular and oval). EDS analysis of metallic parts revealed the pres-
ence mainly of Fe and Ni with smaller amount of Cr.
As it was mentioned above NP is an amorphous, porous volcanic
rock with open channels and rugged surfaces. The glassy phase
structure of the pumice is presented in Fig. 4. It is composed main-
ly of SiO2, whereas feldspars, rich in alkalies (orthoclase, anorthite),
along with minor spheroid hematite were also observed. Its porous
structure has been formed by dissolved gases, during the cooling,
as the lava solidified rapidly through the air. It consists of irregular
or oval shaped and fibrous pores, which are found in closed or open
forms. Their diameter varied between 0.5 lm and 1 mm and some
of them were interconnected and open to the external surface,
forming a network of internal voids.
3.2. Physical and mechanical properties of blended cements
Table 3 presents the variation of blended cements water
demand, setting times and normal mortar flow. The FNS containing
cements demanded relatively less water than the reference, a fact
that was attributed to the delayed hydration of slag. For the mix-
tures containing NP, the decrease is relatively higher, compared
to 100% cement. The flow tests confirmed the above results and
showed that both FNS and NP addition improves the mortar work-
ability. The replacement of cement with the less reactive admix-
tures lead to reduced amounts of hydration products formed
during the early hydration stages, thus resulting to higher work-
ability of the mortar.
All blended cements showed relatively longer setting times,
than the CRef, which generally increase with the increment of the
percentage of the admixtures. The initial and final setting times,
in case of the highest substitution (Cs20, CP20 and CSP20,) were found
to be about 40 min longer than those of reference sample. During
hydration of CRef, the hydration products increased rapidly and
0
-0,02
Carbonates
Differential Relative Weight (%/ oC)
-0,04
Reference
20 wt% FNS
20 wt% NP -0,06
10 wt% FNS & 10 wt% NP
Portlandite
-0,08
-0,1
-0,12
400 500 600 700 800 900
the slurry from the suspending state started to be agglomerated
faster, resulting in shortening of the setting times. The addition
of SCM such as FNS or NP is expected to result in delaying the
hydration process thus increasing setting times, a fact that was
confirmed and by the results of the flow tests. The soundness, mea-
sured according to the Le Chatelier process, was well below the
maximum accepted value of 10 mm [23].
The mortars of the blended cements under investigation were
tested for compressive strengths after 2, 7, 28, 56 and 90 days of
curing and the obtained results are given in Table 4. The results
of the compressive strength of the blended cements with 20% sub-
stitution (CS20, CP20 and CSP20,) are also presented in Fig. 5. In all
cases the blended cements developed relatively lower strength,
at all ages, compared to the reference one. The mixtures containing
only NP reached the compressive strength later than both, refer-
ence sample and FNS mixtures, a fact that should be attributed
to its relative lower pozzolanic activity. As the pozzolanic content
increases, the compressive strengths decrease. After 2 days of
hydration, the compressive strength of the reference sample is
approximately 28% higher (24.1 MPa) than that of the CS20 mixture
(17.2 MPa), whereas the decrease in case of CP20 (16.7 MPa) is
about 30.5%. The corresponding decrease was lower in case of
the CSP20 mixture (17.0 MPa), with 10 wt% FNS and 10 wt% NP,
reaching at 29%, a fact that was expected, because when clinker
in Portland cement is replaced by cementing materials, the mix-
ture produced present lower early strength and longer setting
times [5,8,9]. The rate of strength development of reference
cement depends mainly on its hydration rate, while in case of
the blended cements it also depends on the pure cement phase’s
hydration and the latent hydraulic reactions of FNS and NP. The
same observation was made at 7 days of curing, where the pres-
ence of both FNS and NP resulted in decrease of mortar compres-
sive strength, in inverse proportion to the admixture
replacement ratio.
After 28 days of hydration the compressive strengths were
decreased by 13.1% for FNS, by 15.3% for NP and by 14.0% for
FNS and NP, when the slag and pozzolan content varied from 0
 N. Lemonis et al. / Construction and Building Materials 81 (2015) 130–139 137

Fig. 9. Backscattered electron micrographs of CEM I52.5 pastes after 90 days of curing.

Fig. 10. Backscattered electron micrographs of CS20 pastes after 90 days of curing.

Fig. 11. Backscattered electron micrographs of CP20 pastes after 90 days of curing.

to 20 wt%. At early ages, strength development is governed mostly
by the hydration of cement while the SCM addition does not
appear to contribute in any way to hydration reactions. At later
ages the pozzolanic reaction contributes to strength development,
since it is known to occur at a slower rate than standard cement
hydration [4,5]. Thus, the ‘‘gap’’ in strength between reference
and FNS/NP containing specimens is gradually reducing with
hydration age. At 90 days the compressive strength of the refer-
ence sample is 8% higher (63.5 MPa) than that of the CS20 sample
(58.2 MPa) and approximately 9.6% of CSP20 (57.4 MPa). It should
be noted that all mixtures studied in this work satisfy the require-
ments for the strength class 42.5 as per standard EN 197-1.
3.3. Cement hydration
XRD was used to identify the phases formed during hydration.
Fig. 6 shows the X-ray diffraction patterns of the CSP20 blended
cement (10 wt% of FNS and 10 wt% of NP), hydrated for 2, 7, 28
and 90 days. It can be seen that the main hydration products were
CSH, Ca(OH)2, ettringite (Ca6Al2(SO4)3
32H2O) and carbonate-AFm
phases, as well as unhydrated C3S and C2S. Ettringite was formed
within the first hours of mixing, while Ca(OH)2 remained in the
principal matrix phases up to 7 days of hydration. In this stage,
the main hydration component is C3S. The increased replacement
level of FNS and/or NP led to the Portlandite decrease, especially
138 N. Lemonis et al. / Construction and Building Materials 81 (2015) 130–139
Fig. 12. Backscattered electron micrographs of CP20 pastes after 90 days of curing.
at later ages. The pozzolanic reaction of the SCM used is limited by
the amount of calcium hydroxide produced and by the rate of
amorphous silica dissolution in the alkali environment of the
hydrated cement. The amount of Portlandite increases continuous-
ly at the first days mainly due to the hydration of calcium silicate
phases. However, after 28 days of curing, the rate-production of
crystalline Ca(OH)2 seems to diminish. The amorphous silica from
both FNS and NP reacts with Portlandite, to form CSH gel, which
contributes to the strength of the cement paste. As a result, the
decrease on the evolution of Portlandite is directly related to the
pozzolanic reactions. The peaks of the calcium silicates phases
diminished, especially at the age of 90 days.
X-ray diffraction patterns (Fig. 7) of the blended cements with
20% substitution, together with the reference one, hydrated for
28 days, showed that the main hydration products include Port-
landite (CH) and aluminate phases such as ettringite and carbon-
ate-AFm. Diffraction peaks of the residual calcium silicate phases
were relatively low in all cases, implying that the hydration evolu-
tion has not been delayed by the SCM addition. Lower amount of
Portlandite was detected, suggesting the development of pozzolan-
ic reaction, whereas C2S is the only unhydrated clinker phase still
detected after 28 days of hydration.
Fig. 8 presents the results of TG/DTG of the reference and blend-
ed cements with 20% substitution, hydrated for 28 days. The DTG
curves showed mass loss at about 110, 470 and 710 °C, represent-
ing dehydration of CSH and ettringite, dehydroxylation of Ca(OH)2
and decomposition of calcium carbonate, respectively. The weight
loss of pure reference cement is higher than that of the examined
blended cements, mainly due to the higher evolution of hydration,
which led to the increase of the combined water content. In case of
blended cements the produced Portlandite from the calcium sili-
cate hydration is seems to be consumed during the pozzolanic
reaction at 28 days and secondary CSH gel was produced. The
broad peak in the range 100–150 °C was evidence of the existence
of colloidal CSH gel and ettringite. In case of blended cement it is
observed as a wide band that shifts to lower temperatures, prob-
ably because of the lower crystallinity of the secondary CSH gel
produced from the pozzolanic reaction. The small peak located at
370 °C is due to decomposition of calcium aluminate and alumi-
nosilicate hydrated products and is relatively higher in case of
CS20 blended cement. The third main mass loss can be observed
at around 470 °C, which represents the decomposition of crys-
talline Ca(OH)2 produced by the hydration of calcium silicate phas-
es of the blended cements. The presence of Ca(OH)2 in case of slag
blended cement is seems to be lower, whereas the CP20 and CSP20
blended cements presented similar behavior. In case of reference
cement a noticeably higher peak was observed. The comparatively
smaller peaks of Portlandite, with the wider CSH endothermic
peaks at 110 °C is a confirmation of the increased pozzolanic
reactivity of amorphous SiO2 with the produced lime, after 28 days
of hydration. The intensity of the peaks in the range of 700 °C are
decreased in the case of all blended cements because of the lower
carbonation, since smaller amount of calcium hydroxide was
present.
Figs. 9–12 show backscattered electron micrographs images of
pastes polished sections, after 90 of hydration, for the CRef, CS20,
CP20 and CSP20 blended cements, respectively. In all cases it is pos-
sible to distinguish unreacted anhydrous C2S, with the form of
clusters, and Ca(OH)2, which is slightly darker than anhydrous
clinker phases. CSH can be observed as rim around the anhydrous
phases (inner), or as a hydration product which fills the cementi-
tious matrix (outer). Secondary CSH, from the pozzolanic reaction
of Portlandite with the active silica of FNS and/or NP can be also
observed around those particles with the form of gel. The dark gray
regions forming the matrix mainly consisted of CSH, which forms a
fibrous dense network, in which the unreacted clusters of C2S are
embedded. In case of pure cement phases’ hydration, the CSH
around the clinker phases is much denser and stronger, while the
corresponding, around the amorphous particles of the SCM, is
formed as gelatinous rim, presenting a relatively less uniform
density.
The hydration products, after 90 days of curing, have gradually
filled the network structure and the cement paste structure has
become tight and compact. At the same time, the anhydrous clink-
er phases have been reduced, while in case of 20% substitution,
partially dissolved FNS and/or NP particles, due to the alkali envi-
ronment of the hydrated cement, were detected, presenting a
microstructure with a gelatinous rim of hydration products. Also,
because of the amorphous SiO2 activation, the microstructure of
the cement paste has been modified. The hydration products, espe-
cially low density CSH gel together with some calcium alumi-
nosilicates, are distributed more homogeneously in the space
available, resulting in a more refined pore structure, filling the
pores with simultaneous Ca(OH)2 consumption, thus improving
the mechanical properties of the mortars.
4. Conclusions
Ferronickel slag, a non hazardous waste obtained from reduc-
tive smelting of laterite ore in electric arc furnace, and natural
pumice, both glassy materials, were used as mineral admixtures
up to 20 wt% for the production of blended cements. The slag
and/or pumice containing cements exhibited relatively lower
water demand and longer setting times than the reference speci-
men produced with cement only. Furthermore, the admixtures
addition improved mortar workability.
The blended cements developed strengths at a lower rate com-
pared to the reference sample. The addition of FNS and/or NP
 N. Lemonis et al. / Construction and Building Materials 81 (2015) 130–139
appeared to delay the hydration rate of the produced mixtures at
early ages. At longer ages the pozzolanic reaction appeared to con-
tribute to strength development. The amorphous silicate matrix
was dissolved in the alkali environment of the hydrated cement
and then reacted with Portlandite to form secondary CSH gel. This
led to a modified microstructure of the final hydrated cement
matrix. It must be noted that all cement mixtures satisfied the
requirements for strength class 42.5 as per EN 197-1, whereas,
after 90 days of hydration, all blended cements have developed
more than 90% of the pure reference cement’s strength.
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