International Journal of Minerals, Metallurgy and Materials

Volume 26, Number 5, May 2019, Page 555

https://doi.org/10.1007/s12613-019-1764-2

Replacement of alkali silicate solution with silica fume in

metakaolin-based geopolymers

Ahmed Nmiri1,2), Myriam Duc3), Noureddine Hamdi1), Oumaya Yazoghli-Marzouk4),

and Ezzeddine Srasra1)
1) National Center for Research in Materials Sciences, Technopôle Borj Cedria (CNRSM), Soliman 8027, Tunisia
2) Department of Chemistry, Faculty of Sciences of Tunis, University of Tunis El-Manar, Tunis 2092, Tunisia
3) French Institute of Science and Technology for Transport, Development and Networks (IFSTTAR), Marne-la-Vallée 77447, France
4) Center for Studies and Expertise on Risks, Environment, Mobility and Development (CEREMA), Autun 71404, France
(Received: 31 May 2018; revised: 29 October 2018; accepted: 30 October 2018)

Abstract: A metakaolin (Mk)-based geopolymer cement from Tunisian Mk mixed with different amounts of silica fume (SiO2/Al2O3 molar
ratio varying between 3.61 and 4.09) and sodium hydroxide (10 M) and without any alkali silicate solution, is developed in this work. After
the samples were cured at room temperature under air for 28 d, they were analyzed by X-ray diffraction (XRD), Fourier transform infrared
(FTIR) spectroscopy, environmental scanning electron microscopy, mercury intrusion porosimetry, 27Al and 29Si nuclear magnetic resonance
(NMR) spectroscopy, and compression testing to establish the relationship between microstructure and compressive strength. The XRD,
FTIR, and 27Al and 29Si NMR analyses showed that the use of silica fume instead of alkali silicate solutions was feasible for manufacturing
geopolymer cement. The Mk-based geopolymer with a silica fume content of 6wt% (compared with those with 2% and 10%), corresponding
to an SiO2/Al2O3 molar ratio of 3.84, resulted in the highest compressive strength, which was explained on the basis of its high compactness
with the smallest porosity. Silica fume improved the compressive strength by filling interstitial voids of the microstructure because of its fine
particle size. In addition, an increase in the SiO2/Al2O3 molar ratio, which is controlled by the addition of silica fume, to 4.09 led to a geopo-
lymer with low compressive strength, accompanied by microstructures with high porosity. This high porosity, which is responsible for
weaknesses in the specimen, is related to the amount of unreacted silica fume.

Keywords: metakaolin; silica fume; geopolymer cement; compressive strength

1. Introduction the production of building materials [3]. However, the pro-

The ordinary cement manufacturing process has disastr-
ous effects on the atmosphere and contributes to global
warming through the emission of huge amounts of green-
house gases. Indeed, the conversion of limestone to hydrau-
lic calcium aluminate in the presence of clay requires high
calcination temperatures (approximately 1450°C), contrary
to the maximum 800°C needed to fire the aluminosili-
cate-rich materials (such as kaolinitic clay) required to
produce geopolymer cement. With good mechanical,
fire-retardant [1], and insulating properties [2], geopolymer
cement also ensures huge reductions in CO2 emissions and
is used for the storage of waste, as thermal insulation, and in
Corresponding author: Ahmed Nmiri E-mail: nmiriahmed@gmail.com
© University of Science and Technology Beijing and Springer-Verlag GmbH Germany, part of Springer Nature 2019
duction of geopolymer cement is more expensive than the
production of Portland cement because it requires large
amounts of alkali silicates, which may not be available in
large volumes, as mentioned by Davidovits [3]. Therefore,
the development of geopolymer cements requires the identi-
fication of new sources of alkaline silicates. In this project,
another source of silica—silica fume—was tested to pro-
duce a sustainable geopolymer material with acceptable cost
and no negative effects on the environment by maintaining
the Na2O/SiO2 molar ratio below 0.625 (European Direc-
tives 67/548/EEC and 91/155/EEC) [4].
Among the reactive aluminosilicate precursors mixed
with alkali hydroxide solutions, with or without silicate,
556
fly-ash, blast-furnace slags, and metakaolinite are the most
widespread [5–6]. According to Dupuy et al. [7], heated
materials such as metakaolinite are chosen because heating
the raw material generally promotes the amorphization
process to release silicium and aluminum when they contact
alkaline solutions. Their degree of reactivity for further
production of aluminosiliceous geopolymer materials is thus
increased. The temperature of kaolin calcination required to
produce metakaolin (Mk) varies from one author to another,
ranging from 700°C for 12 h to 800 or 850°C for 2 h [8–10],
which affects Mk reactivity.
According to some authors [11–13], the highest com-
pressive strength of Mk-based geopolymers is obtained
when the Na2SiO3/NaOH mass ratio is approximately 0.20
and the NaOH solution concentration is approximately 10 M.
Silva et al. [14] revealed that the properties of geopoly-
mer systems can be drastically affected by minor changes in
the available SiO2 and Al2O3 concentrations during synthe-
sis. The best resistance of Mk-based geopolymers was ob-
tained when the SiO2/Al2O3 molar ratio was between 3.0
and 3.8. Moreover, the addition of silica fume, which has a
high percentage of SiO2, can improve the geopolymerization
process. Also, this granular stack creates a very dense mi-
crostructure, which results in a compact geopolymer con-
crete with good mechanical characteristics, as demonstrated
by Okoye et al. [15], who studied the effect of silica fume
introduced in fly-ash-based geopolymer concrete with
NaOH (14 M) and sodium silicate as alkali activators. Con-
cretes with silica fume have a reduced porosity [16] and a
low permeability, which leads to substantial resistance to
aggressive attacks under acidic or sulfate-rich solutions, un-
der carbonation, or in alkali silicate reactions [17].
Although silica fume improves mechanical strength, its
quantity in a geopolymer must be optimized. To elucidate
the effects of silica fume on the properties of fly-ash-based
geopolymer, Duan et al. [18] partially replaced fly-ash with
silica fume at levels ranging from 0 to 30wt% in 10% in-
crements. Their results revealed that increasing the silica
fume content enhances the compressive strength, optimizes
the microstructure, and improves the thermal resistance of
the geopolymer. Uysal et al. [19] investigated the effect of
adding silica fume on the physical properties of Mk-based
geopolymer composites. Their results revealed that the addi-
tion of silica fume yielded an improvement in mechanical
strength and abrasion resistance. Dutta et al. [16] studied the
effect of varying the quantity of silica fume (between 2.5%
and 5%) incorporated into fly-ash geopolymer on its poros-
ity and compressive strength. The addition of silica fume in
concentrations as high as 5% improved the compressive
Int. J. Miner. Metall. Mater., Vol. 26, No. 5, May 2019
strength of geopolymer mortars. However, a further increase
of the silica fume concentration caused a decrease in com-
pressive strength because of the accompanying increase in
porosity. Latella et al. [20] also studied the mechanical
properties of a Mk-based geopolymer manufactured with
NaOH, silica fume, and Mk. They demonstrated that poros-
ity is the factor controlling the mechanical properties of the
geopolymers and that compressive strength is more sensitive
to microstructure than to chemical composition.
Rostami and Behfarnia [21] examined the effect of using
silica fume on the permeability of alkali-activated slag con-
crete by substituting three levels of silica fume (5wt%,
10wt%, and 15wt%) for slag. The results showed that in-
creasing the content of silica fume increases the compres-
sive strength and reduces the permeability of the alka-
li-activated slag concrete.
Finally, the third component of the mixture, water, plays
an important role in geopolymer synthesis. Water is essential
to achieve good workability (fluidity) of the geopolymer
cement paste. A high liquid/solid (L/S) ratio improves the
workability of a fresh geopolymer mixture but generally re-
duces its compressive strength. Numerous reports [22–23]
have revealed that a high L/S ratio and high NaOH concen-
tration can accelerate the dissolution of raw materials and
the hydrolysis of Si and Al compounds; however, when the
OH− concentration is sufficiently high (e.g., 12 M), it can
also hinder polycondensation. In fact, larger amounts of
OH− attack the surface of the solid phase, leading to greater
amounts of Si and Al species released into the liquid phase,
which in turn results in a higher compressive strength of the
geopolymer concrete.
In this research, we studied the effect of substituting
2wt%, 6wt%, and 10wt% of Mk with silica fume in a mix-
ture of Mk, silica fume, and sodium hydroxide (without any
alkali silicate solution, as usually used). After evaluating the
effect of silica fume on the mechanical properties of
Mk-based geopolymer cement, we introduce microstructural
and mineralogical considerations to better explain the ob-
served behaviors.
2. Experimental
2.1. Materials
Mk was obtained after natural kaolin from Tabarka (Tu-
nisia) was crushed to 106 μm and calcined at 700°C for 2 h.
The chemical composition and particle size distribution
curve of Mk are given in Table 1 and Fig. 1, respectively.
SiO2 and Al2O3 are the main components, with contents of
63.76wt% and 30.93wt%, respectively. Small amounts of
A. Nmiri et al., Replacement of alkali silicate solution with silica fume in metakaolin-based geopolymers 557

iron and titanium are also present. The granulometric curves has a unimodal distribution, with a single homogeneous
(class distribution and cumulative distribution) of Mk, as population of particles smaller than 124 µm (the average
given by a particle size analyzer, are shown in Fig. 1. Mk particle diameter is approximately 15 µm).
Table 1. Chemical composition of metakaolin wt%
SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O TiO2 SO3 P2O5 LOI
63.76 30.93 1.43 0.11 0.36 0.1 0.88 1.61 0.1 0.12 0.58
Note: LOI⎯Loss on ignition.

Silica fume (Condensil S95DM for concrete applications)

Fig. 1. Particle size distribution on metakaolin powder: class
distribution and cumulative distribution.
was obtained from Sika France. Its chemical composition
(provided by the supplier) is given in Table 2.
Sodium hydroxide solution was obtained by dissolving
dry NaOH powder from Sigma-Aldrich (99% purity) in dis-
tilled water as well as sodium silicate (Na2SiO3, SiO2/Na2O
molar ratio of 2) solution supplied by Fisher Chemicals. Af-
terwards, NaOH solution was used directly or mixed with
the sodium silicate solution using a mechanical mixer at
ambient laboratory temperature and was protected from air
for 24 h before use to ensure that the activator component
was mixed uniformly.

Table 2. Silica fume characteristics from supplier

SiO2 / Apparent density / Real SiC / Free C / Total S / Na2O / BET / Oxide Cl /
wt% (g⋅cm–3) density wt% % wt% wt% (m2⋅g–1) content* / wt% wt%
95 (>92) 0.4–0.45 2.24 1.5 (<3) 1.5 (<3) 0.1 (<0.2) 0.6 (<1) 23 (20–26) 1 (<1.5) 0.06 (<0.2)
Note: *CaO, MgO, Al2O3, and Fe2O3.

2.2. Sample preparation
Mk was dry-mixed with silica fume until a homogeneous
powder was obtained. The resulting blend was then me-
chanically mixed with activators for 4 min. The fresh geo-
polymer paste was then rapidly poured into cylindrical
molds with a 1:2 diameter-to-length ratio [24–25]. All of the
samples were vibrated for 2 min on a vibration table to re-
move trapped air bubbles. Three mixture formulations con-
taining different amounts of silica fume were prepared, with
NaOH solution (10 M, 23.6wt% Na2O, 76.4wt% H2O, and d
= 1.33 g/cm3, where d is the apparent density) used as an acti-
vator. For comparison, Mk-based geopolymers with NaOH (10
M) (without silica fume addition) and with a mixture of NaOH
solution and alkali silicate Na2SiO3 solution (d = 1.04 g/cm3)
were prepared with the ratios given in Table 3. In the mix-
ture B-G, NaOH solution was mixed with Na2SiO3 with a
Na2SiO3/NaOH mass ratio of 0.2 to prepare a liquid alkali
activator; the mixture was prepared 24 h prior to use.

Table 3. Composition of tested metakaolin-based geopolymer mixtures and the corresponding calculated molar ratios (Three sam-
ples were manufactured for each formulation)
Geopolymer Liquid/solid Metakaolin / Silica fume / SiO2/Al2O3 Na2O/SiO2 Na2O/Al2O3 H2O/Na2O
Activators
specimen mass ratio wt% wt% molar ratio molar ratio molar ratio molar ratio
A-G NaOH 0.97 100 0 3.39 0.36 1.22 11.18
B-G NaOH + Na2SiO3 1.11 100 0 3.54 0.35 1.25 13.05
SF1-G NaOH 1.10 98 2 3.61 0.38 1.38 11.36
SF2-G NaOH 1.10 94 6 3.84 0.37 1.44 11.35
SF3-G NaOH 1.10 90 10 4.09 0.37 1.51 11.34

The samples were left at ambient temperature for 24 h electron microscopy (Env. SEM) and mercury intrusion po-
before demolding. Compressive strength was tested after 28 d. rosimetry (MIP). Other fragments for X-ray diffraction
The fragments were then used for environmental scanning (XRD), Fourier transform infrared (FTIR) spectroscopy, and
558 Int. J. Miner. Metall. Mater., Vol. 26, No. 5, May 2019

thermal analysis were further finely crushed in an agate
mortar to pass through an 80-µm sieve.
2.3. Testing methods
The compressive strength of all samples was measured at
20°C after the samples were cured for 28 d at ambient la-
boratory temperature. A compressive strength testing appa-
ratus (EZ50 from AMETEK-LLOYD) was used, with the
displacement rate fixed at 5 mm/min for all of the tests [26].
Compressive strength tests were performed using cylinders
with a 1:2 diameter-to-length ratio [20,24,27]. Three cylind-
ers of each geopolymer were tested, enabling the calculation
of average experimental values.
Thermal analysis (i.e., differential thermal analy-
sis–thermogravimetric analysis (DTA–TGA)) using a Netzsch
STA-409 E apparatus was carried out on hardened paste
from ground geopolymers. Thermal analyses were per-
formed on a mass of 180.8 mg of powder under flowing air.
The functional groups present in the synthesized geopo-
lymers were identified by FTIR spectroscopy (from 4000 to
450 cm−1) using a Perkin Elmer spectrometer 180.
Qualitative mineralogical analyses were performed by
XRD with a Bruker D8 Advance diffractometer equipped
with a copper anode (λCukα1 = 0.154 nm). The XRD patterns
were recorded in a 2θ span of 5° to 80° at a 2θ scanning rate
of 2°/min.
Open porosity measurements were carried out on
freeze-dried samples using a mercury porosimeter (Auto-
pore IV, Micromeritics, France). The structural characteris-
tics of the geopolymers (morphology and particle arrange-
ment) were studied on fresh fractured surfaces from geopo-
lymer specimens using Env. SEM (Quanta 400, FEI, France).
The 27Al and 29Si NMR spectra were acquired using a
600 MHz spectrometer with Bruker UltraShield supercon-
ducting magnet. The sample was placed in a rotor rotating at
the magic angle and at a speed as high as 15 kHz.
3. Results and discussion
3.1. Mineralogical characterization of geopolymers
3.1.1. Thermal analysis
The thermal resistance of SF2-geopolymer was studied
by thermal analysis. Thermal behavior of SF2-G is shown in
Fig. 2.

Fig. 2. Thermal analysis on SF2-G.

The DTA curve shows a large endothermic peak over the

range 25–300°C, with intense mass loss from the sample indi-
cated on the TGA curve. This peak is attributed to the evapora-
tion of free water [28]. The sample mass thereafter remained
relatively constant to temperatures in excess of 1200°C.
The exothermic peak at 898.2°C may correspond to the
transformation of the geopolymer to nepheline and carne-
gieite. These crystalline phases soften and partially melt at
temperatures above 1000°C, characterized by an endother-
mic peak centered at 1160.6°C [29]. The exothermic peak at
966.9°C corresponds to the recrystallization of unpolyme-
rized Mk to spinel [30].
3.1.2. XRD analysis Fig. 3. XRD patterns on metakaolin (Mk) and the geopoly-
Fig. 3 compares the XRD pattern of Mk to that of the mer specimens: A-G, B-G, and SF2-G. I⎯Illite; Q⎯Quartz;
manufactured geopolymer specimens cured at room S⎯Sodium aluminosilicate.
A. Nmiri et al., Replacement of alkali silicate solution with silica fume in metakaolin-based geopolymers
temperature for 28 d. The synthesized geopolymers without
added silica fume (labeled as A-G) or with the
NaOH/Na2SiO3 mixture (labeled as B-G) were faced to the
geopolymer using 10 M NaOH as activator with silica fume.
Because the XRD patterns of the three tested SF-geopolymers
with increasing amount of silica fume were similar, the
SF2-geopolymer pattern shown in Fig. 3 was chosen as a
common representation.
The XRD pattern of Mk consists of a broad peak cen-
tered around 22° (2θ), which indicates the amorphous cha-
racter of Mk. The sharp peaks at 20.85, 26.93, and 50.36°
(2θ) are attributed to quartz, and those at 8.70 and 3.85° (2θ)
are attributed to illite.
The alkaline activation of a dry mixture of Mk with silica
fume caused little change in the XRD pattern of Mk: the large
peak, characterizing the amorphous character of Mk, was dis-
placed from 24° < 2θ < 33° to 28° < 2θ < 40°. This indicates
the partial dissolution of the Mk amorphous particles and
the formation of a new amorphous aluminosilicate phase attri-
buted to the geopolymer systems [22,31]. This broad peak was
present for each formulation and was uniform, irrespective of
the silica fume content (from 0 to 10wt%). The formation of
this new amorphous aluminosilicate phase was also clearly
recognized by FTIR analysis, as discussed below.
In the presence of silica fume, a new small peak was specif-
ically observed at 34.26° (2θ) on the SF-geopolymer specimen
and was attributed to a likely sodium aluminosilicate. The inten-
sity of quartz peaks at 0.333, 0.181, and 0.424 nm and the illite
peak at 0.994 nm remained unchanged before and after activa-
tion, indicating that they did not participate in the reactions.
3.1.3. FTIR analysis
To confirm geopolymer formation, FTIR spectra were
recorded; the results are shown in Fig. 4. As with the XRD
analysis, no difference was observed in the FTIR spectra for
the three FS-geopolymer formulations (therefore, only the
spectrum recorded for the SF2-geopolymer is shown in Fig. 4).
Notably, geopolymers, with or without silica fume and
whatever the alkaline activator, exhibit similar spectra. The
band at approximately 1405 cm−1 is assigned to the vibration
of the C–O bond of sodium carbonate, stemming from the
reaction between NaOH and atmospheric CO2, which in-
duces efflorescence inside materials.
A comparison of the Mk spectrum with that after alkaline
activation, with or without silica fume, shows a shift of the
vibrational band initially at 1093 cm−1 toward a lower wa-
venumber (approximately 1004 cm−1) in the spectra of the
geopolymers. Such behavior is due to the symme-
tric-to-asymmetric stretching mode of T–O–Si (T = Si or Al)
bonds and the depolymerization [32] of original silicate
559
and/or aluminosilicate structures in the Mk, combined with
the substitution of some Si by Al. This depolymerization is
followed by the formation of a tetrahedral framework cha-
racteristic of a geopolymer system. That is, the shift of the
band at 1093 cm−1 indicates dissolution of the Mk amorph-
ous phase in the alkaline-activating solutions and the forma-
tion of a new product as an amorphous aluminosilicate gel
phase [33–34].
Fig. 4. FTIR spectra of metakaolin (Mk) and the geopolymer
specimens: A-G, B-G, and SF2-G (cured at room temperature
for 28 d).
The appearance of new bands at 724 cm−1, attributed to
the symmetric stretching vibrations of Si–O–Si and
Al–O–Si [35–36] is associated with the formation of
amorphous aluminosilicate materials. The band located at
approximately 470 cm−1 is attributed to bending vibrations
of Si–O–Si and O–Si–O bonds [35–36], indicating that
quartz is almost inert in the geopolymerization reaction. By
contrast, the bands in the regions of 1600 and 3450 cm−1,
which are attributed to bending vibrations of H–O–H and
stretching vibrations of –OH, respectively, remain at their
positions observed in the spectrum of Mk.
3.1.4. NMR measurements
To confirm the formation of a geopolymer with a
three-dimensional structure, aluminum and silicon atom speci-
ation was accurately established through 27Al and 29Si magic
angle spinning (MAS) NMR. The spectra of the Mk-based
SF2-geopolymer matrix synthesized with 10 M NaOH and
cured at room temperature for 28 d are presented in Fig. 5(a)
(for 27Al MAS NMR) and Fig. 5(b) (for 29Si MAS NMR).
The other SF-geopolymer matrixes behaved similarly.
The 27Al MAS NMR spectrum shows that the Mk-based
SF2-geopolymer presents a main peak at 60.96 ppm and a
small peak at 3.48 ppm. By contrast, the 29Si MAS NMR
spectrum reveals a wide peak centered between −85.27 and
−86.82 ppm with a shoulder at −91.13 ppm. To interpret the
560
NMR results and in the absence of direct experimental
measurements on Mk, it is important to remember that kao-
linitic clay has essentially aluminum atoms with a coordina-
tion number equal to VI. Thermal treatment of the kaolinitic
clay leads to the formation of IV- and V-coordinate alumi-
num atoms [37]. Thus, the 27A1 MAS NMR spectra of Mk
usually present three signals centered at 0, 30, and 60 ppm.
Many studies [3,37] have assigned the signal at 0 or 60 ppm
Fig. 5. (a) 27Al MAS NMR and (b) 29Si MAS NMR spectra of a metakaolin-based SF2-geopolymer. δ⎯Chemical shift.
The experimental results in Fig. 5 are consistent with
such behavior. The SF2-geopolymer contains AlQ4(4Si)
coordination characterized by the peak centered at 60.96
ppm (>60 ppm), and trace amounts of Al(VI) characterized
by the small peak centered at 3.48 ppm (the position of this
peak did not increase, as expected on the basis of the litera-
ture). The presence of a clear peak near 3.48 ppm means that
unreacted Mk may be present (perhaps because of insufficient
concentration of NaOH set at 10 M). Singh et al. [38] have
reported a similar result.
For the 29Si MAS NMR, the spectra of kaolinitic clay and
Mk consist of a single resonance peak at −91.5 ppm as-
signed to the SiQ3(3Si) coordination [37,39–40]. By contrast,
the Mk-based geopolymer usually presents a broad peak
centered at −94.5 ppm assigned to the SiQ4(mAl) coordina-
tion [3]. The experimental results differ from those reported
in the literature. Whereas the shoulder observed at −91.13
ppm could be associated with unreacted Mk (as observed in
the 27Al MAS NMR spectrum), the peak associated with the
SiQ4(3Al) coordination was positioned at −85.27 ppm [3].
3.2. Physical characterization of SF-geopolymers
3.2.1. Compressive strength
Compressive strength has been used by many re-
searchers [14,41] as a tool for confirming the success of
geopolymerization. The compressive strengths of the tested
geopolymer specimens are shown in Fig. 6 (values are av-
erage measurements calculated from three replicates).
The specimen with the highest compressive strength after
curing for 28 d (SF2-G) contains 6wt% silica fume and with
Int. J. Miner. Metall. Mater., Vol. 26, No. 5, May 2019
to Al(VI) or Al(IV) respectively, whereas Al(V) should re-
sonate at 30 ppm. After geopolymerization, the geopolymer
matrixes usually contain chemical shifts of not only
AlQ4(4Si) (Al linked to four Si atoms via four oxygens) but
also of SiQ4(mAl) (Si linked to m Al atoms via four oxy-
gens), with 0 ≤ m ≤ 4 [3]. In the Mk-based geopolymer, the
main chemical shift of aluminum at approximately 55–60
ppm corresponds to AlQ4(4Si) [3].
a SiO2/Al2O3 molar ratio of 3.84. It reaches 35.00 MPa,
whereas the lowest compressive strength is 14.47 MPa,
which corresponds to the geopolymer mixture with 10% si-
lica fume (SF3-G). In this case, the SiO2/Al2O3 ratio is 4.09.
An intermediate compressive strength was obtained for
SF1-G with 2% silica fume and SiO2/Al2O3 = 3.61. These
results demonstrate the existence of an optimum silica fume
content of approximately 6%. In parallel, the compressive
strengths of the Mk-based geopolymers without added silica
fume and with NaOH (in A-G) and NaOH/Na2SiO3 (in B-G)
as activators with SiO2/Al2O3 = 3.39 and 3.54, respectively,
reached 33.75 MPa and 20.42 MPa, respectively. Replacing
a fraction of the Mk (requiring energy for production) with
silica fume (an industrial byproduct) gives almost the same
mechanical performance.
Fig. 6. Compressive strength of geopolymer specimens: A-G,
B-G, SF1-G, SF2-G, and SF3-G (cured at room temperature for
28 d).
A. Nmiri et al., Replacement of alkali silicate solution with silica fume in metakaolin-based geopolymers
The addition of Na2SiO3 to NaOH in the B-G specimen
failed to give higher compressive strength than that meas-
ured on the A-G or SF2-G specimens. In fact, the addition
of sodium silicate to the NaOH solution increases the vis-
cosity of the total solution and reduces the flow of the
geopolymer [42]. Thus, the reaction is incomplete and the
dissolution of aluminosilicate is insufficient. The paste har-
dens quickly, meaning that part of the Mk particles remain
unreacted and the polycondensation process is slow, requir-
ing the addition of water to increase geopolymer paste flo-
wage. Therefore, the contact between the activation solution
and the Mk particles is limited because of the large volume
of liquid used, which weakens the compressive strength of
the geopolymer. A high L/S ratio improves the workability
of a fresh geopolymer mixture, but reduces its compressive
strength [22,34]. According to Zhang et al. [43], as little
water as possible should be added to ensure high mechanical
strength and excellent durability.
These results also confirm the importance of the SiO2/Al2O3
molar ratio, which affects the compressive strength of the
The morphology and particle size of the A-G geopolymer
varies after the addition of sodium silicate to NaOH, as ob-
served for the B-G geopolymer. The A-G fractured surface
reveals a denser matrix with fine particles, whereas the B-G
material develops a heterogeneous matrix with larger par-
ticles and higher porosity. This difference contributes to the
decrease in compressive strength (from 33.75 MPa for A-G
to 20.42 MPa for B-G).
In the case of the SF-geopolymers, condensation appears
to be higher. Silica fume, because of its small size (around
561
hardened geopolymer. Generally, a low SiO2/Al2O3 ratio
(below 3.4) leads to low-strength products accompanied by
a microstructure with more Na–Al–Si grains rather than
amorphous Na–Al–Si, which is associated with geopolymers.
By contrast, an increase in the SiO2/Al2O3 molar ratio to 3.4
or 3.8 is strongly related to the improvement in compressive
strength [14,44]. Such results agree with those of Bernal
et al. [27], who studied the effect of granulated blast-furnace
slag addition on the compressive strength of Mk-based
geopolymer. They tested SiO2/Al2O3 molar ratios of 3.0, 3.4,
3.8, and 4.0 with NaOH/Na2SiO3 as an alkaline activator
and found that formulations with SiO2/Al2O3 ratios between
3.4 and 4.0 exhibited the highest compressive strengths.
3.2.2. SEM observation
The Env. SEM technique was used to study variations in
the texture (particle organization) and porosity (density) of
geopolymer materials as the amount of silica fume added to
a geopolymer mixture was varied. Fig. 7 shows the SEM
micrographs of the geopolymer specimens cured at room
temperature for 28 d.
Fig. 7. SEM micrographs of geopo-
lymer test specimens cured at room
temperature for 28 d: (a) A-G; (b) B-G;
(c) SF1-G; (d) SF2-G; (e) SF3-G.
0.2 µm), helps reduce the volume of voids, which directly
affect geopolymer strength. The density and porosity in
SF-geopolymers, however, cannot be quantified from Env.
SEM images, nor can the presence or absence of unreacted
Mk and silica particles [45]. No significant differences in
microstructures between the three geopolymers (SF1-G,
SF2-G, and SF3-G) were clearly observed.
3.2.3. MIP analysis
To obtain a more quantitative image of the microstructure,
MIP was used to complement the Env. SEM observations and
562
to explain the effect of silica fume on the mechanical proper-
ties of Mk-based geopolymers. Under the assumption of a
regular pore geometry and pore interconnection, we measured
porosity by the volume of mercury intruded into freeze-dried
hardened specimens. Each incremental pressure corresponds
to a pore diameter and a total porosity is determined from
Table 4. Physical proprieties of geopolymers determined through mercury intrusion porosimetry
Geopolymer Total intrusion volume / Pore diameter of the main pore
specimen (mL⋅g–1) family / nm
A-G 0.20 174
B-G 0.25 445–500
SF1-G 0.18 195
SF2-G 0.21 220
SF3-G 0.24 250
Fig. 8. MIP curves of A-G, B-G, SF1-G, SF2-G, and SF3-G
geopolymer specimens.
The mercury intrusion curves of all geopolymers are
characterized by unimodal behavior with a major population
of macropores (defined by the International Union of Pure
and Applied Chemistry as pores larger than 50 nm). How-
ever, the position of the peak characterizing the most com-
mon pore size within the pore families shifts with the type
of geopolymer mixture. As observed by Env. SEM, the
geopolymer B-G presents a pore family with the largest pore
size, centered at 445–500 nm. In comparison, the A-G and
SF-geopolymers display mainly smaller pores, centered
between 174 and 250 nm.
The addition of silica fume affects the SiO2/Al2O3 molar
ratios, which strongly influence the mechanical properties of
the geopolymers. The mercury intrusion curves of samples
of SF1-G, SF2-G, and SF3-G with corresponding
SiO2/Al2O3 molar ratios of 3.61, 3.84, and 4.09, respectively,
show that a substantial change in pore size accompanied the
change in the SiO2/Al2O3 molar ratio. As shown in Fig. 8,
the mercury intrusion curve of SF3-G, which exhibited the
lowest compressive strengths, presents a pore family with
the highest pore size among the SF-geopolymers, centered
Int. J. Miner. Metall. Mater., Vol. 26, No. 5, May 2019
the total volume intruded. The physical properties of geo-
polymer calculated from MIP analysis are given in Table 4.
Additionally, Fig. 8 shows the pore size density function
(corresponding to the differential calculation of the intruded
volume of mercury (dV) versus the logarithm of pore di-
ameter (dlgD)) versus the pore diameter in the geopolymers.
Calculated apparent particle density /
Total porosity / %
(g⋅cm–3)
2.20 30.6
2.24 36.2
2.15 28.6
2.22 31.6
2.16 33.7
at 250 nm, which is linked to the amount of unreacted ma-
terial in the specimens. Furthermore, particle morphology
and the arrangement and porosity are key microstructural
parameters that govern the mechanical properties of the
geopolymers, irrespective of precursor type or mixture
composition, as noted by Latella et al. [20]. The develop-
ment of compressive strength is related to the evolution of
pore structure [46]. Here the increase in pore diameter of the
B-G and SF3-G geopolymers (measured as 445–500 and
250 nm, respectively) and their total porosity (evaluated as
36.2 and 33.7%, respectively) are correlated to the decrease
in compressive strength compared to those of the SF2-G and
A-G geopolymers. The lower mechanical strength of the
SF1-G geopolymer, even though it displayed the lowest po-
rosity, must be explained by other means.
4. Conclusions
The aim of this work was to study the feasibility of re-
placing the alkali silicate solution usually added to
Mk-based geopolymer paste with silica fume. The proper-
ties of SF-geopolymers with 2, 6, or 10wt% of silica fume
activated by NaOH were compared with those of geopoly-
mers without added silica fume (A-G geopolymer) or acti-
vated with NaOH mixed with Na2SiO3 (B-G geopolymer).
The FTIR spectra of the SF-geopolymers revealed a band
shift from 1093 cm−1 (in the spectrum of Mk) to ~1004 cm−1
(in the spectra of geopolymers). A displacement of the broad
peak from 24° < 2θ < 33° to 28° < 2θ < 40° was also ob-
served in the XRD patterns. Moreover, the 29Si and 27Al
MAS NMR spectra of the SF-geopolymers showed chemi-
cal shifts at approximately −85.27 ppm and 60.96 ppm, cor-
responding to SiQ4(3Al) and AlQ4(4Si) coordination, re-
A. Nmiri et al., Replacement of alkali silicate solution with silica fume in metakaolin-based geopolymers
spectively. These latter three results indicated the formation
of geopolymer material.
The mechanical properties of the geopolymers were cor-
related with their microstructural characteristics to explain
the various behaviors observed in the specimens. The mor-
phology (observed by Env. SEM) and porosity (given by
MIP) are the main microstructural characteristics determin-
ing the compressive strength of the SF-geopolymers, along
with the SiO2/Al2O3 molar ratio, porosity level, and pore
diameter. The highest compressive strength (35 MPa) was
attained with the addition of 6wt% silica fume (the
SiO2/Al2O3 molar ratio was 3.84), Finally, on the basis of
observations of the physical, microstructural, and thermal
properties, the silica fume geopolymers were found to be
much more sustainable than sodium silicate geopolymers.
Acknowledgement
The authors are pleased to acknowledge the Tunisian
Ministry of Higher Education and Scientific Research for its
help in financing internships in France.
References
[1] M. Mustafa, A. Bakri, H. Mohammed, H. Kamarudin, I.K.
Niza, and Y. Zarina, Review on fly ash-based geopolymer
concrete without Portland Cement, J. Eng. Technol. Res.,
3(2011), No. 1, p. 1.
[2] M.A. Villaquirán-caicedo, R.M. de Gutiérrez, S. Sulekar, C.
Davis, and J.C. Nino, Thermal properties of novel binary
geopolymers based on metakaolin and alternative silica
sources, Appl. Clay Sci., 118(2015), p. 276.
[3] J. Davidovits, Properties of geopolymer cements, [in] First
International Conference on Alkaline Cements and Con-
cretes, Kiev, 1994, p. 131.
[4] H.T. Huynh, New generation geopolymers, [in] 2nd French
Seminar on Geopolymers, Clermont-Ferrand, 2013.
[5] Y.M. Liew, C.Y. Heah, A.B. Mohd Mustafa, and H. Kama-
rudin, Structure and properties of clay-based geopolymer ce-
ments: A review, Prog. Mater. Sci., 83(2016), p. 595.
[6] P. Zhang, Y.X. Zheng, K.J. Wang, and J.P. Zhang, A review
on properties of fresh and hardened geopolymer mortar,
Composites Part B, 152(2018), p. 79.
[7] C. Dupuy, A. Gharzouni, N. Texier-Mandoki, X. Bourbon,
and S. Rossignol, Thermal resistance of argillite-based alka-
li-activated materials. Part 1: Effect of calcination processes
and alkali cation, Mater. Chem. Phys., 217(2018), p. 323.
[8] M.I. Khan, H.U. Khan, K. Azizli, S. Sufian, Z. Man, A.A.
Siyal, N. Muhammad, and M.F. ur Rehman, The pyrolysis
kinetics of the conversion of Malaysian kaolin to metakaolin,
Appl. Clay Sci., 146(2017), p. 152.
[9] J.S. Geng and Q. Sun, Effects of high temperature treatment
563
on physical-thermal properties of clay, Thermochim. Acta,
666(2018), p. 148.
[10] V. Medri, S. Fabbri, J. Dedecek, Z. Sobalik, Z. Tvaruzkova,
and A. Vaccari, Role of the morphology and the dehydrox-
ylation of metakaolins on geopolymerization, Appl. Clay Sci.,
50(2010), No. 4, p. 538.
[11] Y.M. Liew, H. Kamarudin, A.M. Mustafa Al Bakri, M.
Luqman, I. Khairul Nizar, C.M. Ruzaidi, and C.Y. Heah,
Processing and characterization of calcined kaolin cement
powder, Constr. Build. Mater., 30(2012), p. 794.
[12] Y.M. Liew, H. Kamarudin, A.M. Mustafa Al Bakri, M. Bin-
hussain, M. Luqman, I. Khairul Nizar, C.M. Ruzaidi, and
C.Y. Heah, Influence of solids-to-liquid and activator ratios
on calcined kaolin cement powder, Phys. Procedia, 22(2011),
p. 312.
[13] C.Y. Heah, H. Kamarudin, A.M. Mustafa Al Bakri, M.
Bnhussain, M. Luqman, I. Khairul Nizar, C.M. Ruzaidi, and
Y.M. Liew, Kaolin-based geopolymers with various NaOH
concentrations, Int. J. Miner. Metall. Mater., 20(2013), No. 3,
p. 313.
[14] P. De Silva, K. Sagoe-Crenstil, and V. Sirivivatnanon, Kinet-
ics of geopolymerization: Role of Al2O3 and SiO2, Cem.
Concr. Res., 37(2007), No. 4, p. 512.
[15] F.N. Okoye, J. Durgaprasad, and N.B. Singh, Effect of silica
fume on the mechanical properties of fly ash
based-geopolymer concrete, Ceram. Int., 42(2015), No. 2, p.
3000.
[16] D. Dutta, S. Thokchom, P. Ghosh, and S. Ghosh, Effect of si-
lica fume additions on porosity of fly ash geopolymers, J.
Eng. Appl. Sci., 5(2010), No. 10, p. 74.
[17] C.S. Poon, S.C. Kou, and L. Lam, Compressive strength ,
chloride diffusivity and pore structure of high performance
metakaolin and silica fume concrete, Constr. Build. Mater.,
20(2006), No. 10, p. 858.
[18] P. Duan, C.J. Yan, and W. Zhou, Compressive strength and
microstructure of fly ash based geopolymer blended with si-
lica fume under thermal cycle, Cem. Concr. Compos.,
78(2017), p. 108.
[19] M. Uysal, M.M. Al-mashhadani, Y. Aygörmez, and O. Can-
polat, Effect of using colemanite waste and silica fume as
partial replacement on the performance of metakaolin-based
geopolymer mortars, Constr. Build. Mater., 176(2018), p.
271.
[20] B.A. Latella, D.S. Perera, D. Durce, E.G. Mehrtens, and J.
Davis, Mechanical properties of metakaolin-based geopoly-
mers with molar ratios of Si/Al ≈ 2 and Na/Al ≈ 1, J. Mater.
Sci., 43(2008), No. 8, p. 2693.
[21] M. Rostami and K. Behfarnia, The effect of silica fume on
durability of alkali activated slag concrete, Constr. Build.
Mater., 134(2017), p. 262.
[22] D. Panias, I.P. Giannopoulou, and T. Perraki, Effect of syn-
thesis parameters on the mechanical properties of fly
ash-based geopolymers, Colloids Surf. A, 301(2007), No. 1-3,
p. 246.
[23] Z.H. Zhang, X. Yao, H.J. Zheng, and C. Yue, Role of water
564
in the synthesis of calcined kaolin-based geopolymer, Appl.
Clay Sci., 43(2009), No. 2, p. 218.
[24] J.G.S. van Jaarsveld and J.S.J. van Deventer, Effect of the al-
kali metal activator on the properties of fly ash based geopo-
lymers, Ind. Eng. Chem. Res., 38(1999), No. 10, p. 3932.
[25] P.N. Lemougna, A.B. Madi, E. Kamseu, U.C. Melo, M.P.
Delplancke, and H. Rahier, Influence of the processing tem-
perature on the compressive strength of Na activated lateritic
soil for building applications, Constr. Build. Mater.,
65(2014), p. 60.
[26] A.M.M. Al Bakri, H. Kamarudin, M. Bnhussain, J. Liyana,
and C.M. Ruzaidi Ghazali, Nano geopolymer for sustainable
concrete using fly ash synthesized by high energy ball mil-
ling, Appl. Mech. Mater., 313-314(2013), p. 169.
[27] S.A. Bernal, E.D. Rodríguez, R. Mejía de Gutiérrez, M. Gor-
dillo, and J.L. Provis, Mechanical and thermal characterisa-
tion of geopolymers based on silicate-activated metakao-
lin/slag blends, J. Mater. Sci., 46(2011), No. 16, p. 5477.
[28] T. Revathi, R. Jeyalakshmi, and N. P. Rajamane, Study on
the role of n-SiO2 incorporation in thermo-mechanical and
microstructural properties of ambient cured FA-GGBS geo-
polymer matrix, Appl. Surf. Sci., 449(2018), p. 322.
[29] C. Kuenzel, L.M. Grover, L. Vandeperre, A.R. Boccaccini,
and C.R. Cheeseman, Production of nepheline/quartz ceram-
ics from geopolymer mortars, J. Eur. Ceram. Soc., 33(2013),
No. 2, p. 251.
[30] G. Kakali, T. Perraki, S. Tsivilis, and E. Badogiannis, Ther-
mal treatment of kaolin: The effect of mineralogy on the
pozzolanic activity, Appl. Clay Sci., 20(2001), No. 1-2, p. 73.
[31] S. Ahmari, X. Ren, V. Toufigh, and L.Y. Zhang, Production
of geopolymeric binder from blended waste concrete powder
and fly ash, Constr. Build. Mater., 35(2012), p. 718.
[32] W.K.W. Lee and J.S.J. van Deventer, Use of infrared spec-
troscopy to study geopolymerization of heterogeneous
amorphous aluminosilicates, Langmuir, 19(2003), No. 21, p.
8726.
[33] Q. Wan, F. Rao, S.X. Song, D.F. Cholico-González, and N.L.
Ortiz, Combination formation in the reinforcement of meta-
kaolin geopolymers with quartz sand, Cem. Concr. Compos.,
80(2017), p. 115.
[34] K. Gao, K.L. Lin, D.Y. Wang, H.S. Shiu, C.L. Hwang, and
T.W. Cheng, Effects of nano-SiO2 on setting time and com-
pressive strength of alkali- activated metakaolin-based geo-
Int. J. Miner. Metall. Mater., Vol. 26, No. 5, May 2019
polymer, Open Civ. Eng. J., 7(2013), p. 84.
[35] W.K.W. Lee and J.S.J. van Deventer, Structural reorganisa-
tion of class F fly ash in alkaline silicate solutions, Colloids
Surf. A, 211(2002), No. 1, p. 49.
[36] T. Bakharev, Geopolymeric materials prepared using Class F
fly ash and elevated temperature curing, Cem. Concr. Res.,
35(2005), No. 6, p. 1224.
[37] J. Rocha and J. Klinowski, 29Si and 27Al mag-
ic-angle-spinning NMR studies of the thermal transformation
of kaolinite, Phys. Chem. Miner., 17(1990), No. 2, p. 179.
[38] P.S. Singh, M. Trigg, I. Burgar, and T. Bastow, Geopolymer
formation processes at room temperature studied by 29Si and
27
Al MAS-NMR, Mater. Sci. Eng. A, 396(2005), No. 1-2, p.
392.
[39] F. Škvára, L. Kopecký, J. Němeče k, and Z. Bittnar, Micro-
structure of geopolymer materials based on fly ash, Ceram.
Silik., 50(2006), No. 4, p. 208.
[40] A. Bourlon, Physico-chimie et Rhéologie de Géopolymères
Frais Pour la Cimentation des Puits Pétroliers [Dissertation],
Pierre et Marie Curie University, Paris, 2010.
[41] M.A. Soleimani, R. Naghizadeh, A.R. Mirhabibi, and F. Go-
lestanifard, Effect of calcination temperature of the kaolin
and molar Na2O/SiO2 activator ratio on physical and micro-
structural properties of metakaolin based geopolymers, Iran.
J. Mater. Sci. Eng., 9(2012), No. 4, p. 43.
[42] P. Chindaprasirt, T. Chareerat, and V. Sirivivatnanon, Wor-
kability and strength of coarse high calcium fly ash geopoly-
mer, Cem. Concr. Compos., 29(2007), No. 3, p. 224.
[43] Y.S. Zhang, W. Sun, and Z.J. Li, Composition design and
microstructural characterization of calcined kaolin-based
geopolymer cement, Appl. Clay Sci., 47(2010), No. 3-4, p.
271.
[44] C.K. Ma, A.Z. Awang, and W. Omar, Structural and material
performance of geopolymer concrete: A review, Constr.
Build. Mater., 186(2018), p. 90.
[45] T. da S. Rocha, D.P. Dias, F.C.C. França, R.R. de S. Guerra,
and L.R. da C. de O. Marques, Metakaolin-based geopolymer
mortars with different alkaline activators (Na+ and K+),
Constr. Build. Mater., 178(2018), p. 453.
[46] P. Duan, Z.G. Shui, W. Chen, and C.H. Shen, Effects of me-
takaolin , silica fume and slag on pore structure, interfacial
transition zone and compressive strength of concrete, Constr.
Build. Mater., 44(2013), p. 1.