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Ceramics International
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Mechanochemical and thermal activation of kaolin for manufacturing

geopolymer mortars – Comparative study
Ida Balczár n, Tamás Korim, András Kovács, Éva Makó
Institute of Materials Engineering, University of Pannonia, H-8201 Veszprém, P.O. Box 158, Hungary

art ic l e i nf o a b s t r a c t

Article history: The present study compares two different activating methods of kaolin for the purpose of manufacturing
Received 31 March 2016 a binding material for geopolymer mortar production. Thermal activation is a well-known procedure, but
Received in revised form here, the investigation focused on the influence of heat-treatment temperature and time. In this case a
27 June 2016
new method, called mechanochemical activation, was applied in parallel using various grinding para-
Accepted 27 June 2016
meters (grinding time, the mass ratio of sample to grinding body, and rotation speed). The structural and
morphological changes of thermally and mechanochemically activated kaolinite were followed by X-ray
Keywords: diffraction (XRD), thermal analysis, and Fourier transform infrared (FTIR) spectrometry, scanning electron
A. Calcination microscopy (SEM), as well as determination of specific surface area and particle size distribution. The
A. Milling
effectiveness of thermal and mechanochemical activation was characterised by compressive strength at
C. Mechanical properties
28 days and a calculated “degree of amorphisation”. The results demonstrate that mechanochemical
Geopolymer mortar
activation is an effective method for producing geopolymers, the maximum compressive strength
(55.6 MPa) of mechanochemically activated samples surpassed the best thermally activated one
(43.0 MPa).
& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

1. Introduction metakaolinite, in its double-layer structure [7] and pozzolanic

Industrial utilisation of kaolins covers a wide range of appli-
cations including the production of ceramics, paper, paints, plas-
tics, rubber, ink, cracking catalysts and adsorbents, depending on
the physical, chemical, structural, and surface properties of kaoli-
nites [1]. One of the rapidly developing application areas is of in-
organic polymers (geopolymers) [2,3], where kaolin plays an im-
portant part as raw material. Geopolymers can provide compar-
able performance to traditional cementitious binders in a range of
applications, but with the added advantage of significantly re-
duced greenhouse emissions [4] due to their distinct manu-
facturing process. Raw materials commonly used for geopolymer
synthesis are those which are rich in alumino-silicates such as
natural pozzolans, fly ashes, blast furnace slags, and calcined
kaolins [1].
Calcined kaolinite, namely metakaolinite, is essentially an an-
hydrous alumino-silicate obtained by the heat treatment of kao-
linite. Due to its disordered structure, it possesses a huge reactive
potential when activated in alkali solution [5]. Many papers focus
on the conditions [6,8,12–14] of the calcination, such as the in-
fluence of the calcination temperature, which induce changes in
n
Corresponding author.
E-mail address: balczari@almos.uni-pannon.hu (I. Balczár).
activity [8]. Also, studies have shown the effect of impurities [9,10]
in kaolin and the role of residual water [11] on properties of
geopolymers. In summary, the ideal temperature for calcination of
kaolin was proved to be 700–750 °C [6,13,14], whilst it was ob-
served that kaolin containing as high as 30 wt% minor minerals
(e.g. illite, quartz) is still suitable for geopolymerisation [10] or
even improve the formation of metakaolinite [9]. Nevertheless the
influence of heat treatment time on the reactivity of metakaolinite
has not been investigated in the literature.
The physical, chemical, structural and surface properties of
kaolinite can be significantly modified by mechanochemical acti-
vation through dry grinding [15–18]. It has been found that
grinding of kaolinite causes distortion of the kaolinite lattice,
whereas prolonged dry grinding results in a disordered phase,
which yields an amorphous material due to the complete de-
struction of the kaolinite structure [15]. It also means that during
grinding surface energy increases and hence so does chemical
reactivity [16,18].
Calcination (thermal activation) of kaolin was so far the only
used method to activate kaolin for geopolymer synthesis, despite
of the fact mechanochemical activation is a well known technique
in case of fly ash based geopolymers [19–21]. The aim of this study
was to explore the options of mechanochemical activation and
compare it with the thermal activation. In this paper, a detailed
structural and morphological comparison of activated kaolin

http://dx.doi.org/10.1016/j.ceramint.2016.06.182
0272-8842/& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: I. Balczár, et al., Mechanochemical and thermal activation of kaolin for manufacturing geopolymer mortars –
Comparative study, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.182i
2 I. Balczár et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎
samples is presented. In addition, we want to highlight the ap-
plicability of the derived number “degree of amorphisation” and
compressive strength to characterise the reactivities of differently
activated kaolin samples.
2. Materials and methods
2.1. Materials
Natural, high-grade kaolin from Sedlec in the Czech Republic
was used in this experiment. Its chemical composition in weight
percent is SiO2: 46.23; Al2O3: 36.74; TiO2: 0.05; Fe2O3: 0.88; CaO:
0.80; MgO: 0.28; K2O: 0.66; loss on ignition: 13.36. The major
mineral constituent is medium-defect kaolinite (92 wt%) with a
Hinckley index [22] of around 0.7. Some quartz (4 wt%) and
muscovite (4 wt%) are also present as minor constituents. This
kaolin was selected for the experiment because of its high kaoli-
nite content. The specific surface area of Sedlec kaolin was
19.4 m2/g. Its medium value of the particle size distribution (D50)
determined by a Fritsch Laser Particle Sizer “Analysette 22” is
6.6 mm. The kaolin contained 10.1% of particles less than 1 mm and
10.9% of particles greater than 20 mm in size. The derivative ther-
mogravimetric (DTG) curve of the untreated kaolin can be seen in
Fig. 1, which indicates that dehydroxylation of kaolinite starts
around 500 °C, and ends at around 700 °C. The DTG peak tem-
perature of dehydroxylation is 569 °C. The adsorbed and structural
water content of kaolin were 1.52 wt% and 13.35 wt%, respectively.
Laboratory-grade sodium hydroxide pellets and sodium silicate
(28.6 wt% SiO2, 6.8 wt% Na2O, 64.6 wt% H2O) were used as alkaline
activators. Standard quartz sand (Lasselsberger-Knauf) was added
as aggregate for the preparation of geopolymer mortars. The
maximum grain size of standard sand was 2 mm.
2.2. Sample preparation
Considering the DTG curve of untreated kaolin, thermal acti-
vation was carried out by calcining the kaolin at 500, 550, 600 and
700 °C, for a much shorter time (1 h and 3 h) than generally used
[6,11,13] (8 h), in a programmable electric furnace using a heating
rate of 5 °C/min. Hereafter, thermal activated samples will be re-
ferred to as TA.
Mechanochemical activation was accomplished by using a
Fritsch Pulverisette 6 type planetary ball mill. Each milling was
carried out with 50 g sample in a 500 cm3 zirconia grinding bowl
using zirconia balls (10 mm diameter). Various grinding para-
meters (grinding time, rotation speed, and the mass ratio of
Differential mass loss
569 °C
0 200 400 600
Temperature (°C)
Fig. 1. DTG curve of untreated kaolin.
Please cite this article as: I. Balczár, et al., Mechanochemical and thermal activation of kaolin for manufacturing geopolymer mortars –
Comparative study, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.182i
Table 1
Grinding parameters of MA samples.
Mass ratio of sample to Rotation speed of the Grinding time
grinding body (ms:mgb) mill (rpm) (min  1) (min)
1:8 500 15
1:14 500 15
1:11 60
120
400
180
240
15
45
500 60
75
105
15
30
600
50
80
sample to grinding body) were used during the experiment.
Grinding time was increased from 15 min to 300 min. The applied
rotation speeds were 400, 500, and 600 rpm. Samples were
ground at 1:8, 1:11, and 1:14 the mass ratio of sample to grinding
body (ms:mgb) (Table 1). Hereafter, mechanochemical activated
samples will be referred to as MA.
Geopolymer sample manufacturing was based on that of
standard cement mortars (EN 196-1). Composition of geopolymer
and treatment-conditions of the mortar was chosen according to
literatures [23,24] and a previous study [25] and were the same for
thermally and mechanochemically activated samples. The molar
ratios of the geopolymer binder were as follows: SiO2/Al2O3 ¼3.6,
Na2O/Al2O3 ¼1.0, H2O/Al2O3 ¼ 14.4. The geopolymer binder con-
tains 39.5 g TA sample including 4.5 g destilled water or 39.5 g MA
sample (without any distilled water), 48.9 g waterglass and 7.3 g
NaOH pellet. (Note that TA samples were supplemented with the
same quantity of destilled water (4.5 g) as the structural water
content of kaolin, to overcome the lack of water content in TA
samples.) Firstly NaOH pellet was dissolved in waterglass (and
distilled water), then this activator solution was mixed mechani-
cally (800 min  1) with the MA and TA samples for 1 min. After
that quartz sand was added to this geopolymer binder as ag-
gregate (with a 1:2 kaolin:sand mass ratio) and the mortar was
kept mixing until homogenised. Finally, the entrained air was re-
moved by tapping the mixing bowl to the bench, and the mortar
was cast into cylindrical moulds of dimensions Ø30 mm  30 mm.
The prepared fresh mortars were allowed to rest at room tem-
perature for 45 min, and then cured in a laboratory oven at 65 °C
for 2 h [26]. The hardened mortars were de-moulded at 1 day of
age and stored at ambient temperature in laboratory atmosphere
(21 °C and 62% relative humidity) until testing at 28 days of age.
2.3. Methods
2.3.1. X-Ray powder diffraction (XRD)
The XRD analyses were carried out using a Philips PW 3020
vertical goniometer equipped with curved graphite diffracted
beam monochromator at room temperature. The radiation applied
was CuKα from a long fine focus Cu tube, operating at 50 kV and
40 mA. The samples were measured in step scan mode with steps
of 0.02° 2θ and a counting time of 1 s. Data collection was per-
800 1000
formed with X′Pert Data Collector. X′PertHigh Score Plus software
was applied to identify XRD patterns and to determine the integral
intensity of an individual diffraction peak.
A so-called “degree of amorphisation” (hereafter referred to as

Intensity (arbitrary unit)
(a)
(b)
(c)
(d)
(e)
5 10
Fig. 2. XRD patterns of untreated kaolin (a) and TA samples heat-treated (b) at 500 °C for 1 h, (c) at 500 °C for 3 h, (d) at 700 °C for 1 h and (e) at 700 °C for 3 h. (k: kaolinite
PDF 14-164; m: muscovite PDF7-25; q: quartz PDF33-1161).
DOA) was used to characterise the effectiveness of thermal and
mechanochemical activation through the amount of amorphous
kaolinite or metakaolinite phase. DOA was calculated using the
integral intensities of the main peak of kaolinite (7.2 Å) before
(Anot activated) and after (Aactivated) thermal and mechanochemical
treatment with Eq. (1).
⎛ A ⎞ The microstructure of kaolin samples was characterised using a
degree of amorphisation ( DOA)( %)=100−⎜ activated ∙100⎟
⎝ A notactivated ⎠
2.3.2. Particle size distribution and specific surface area
Particle size distributions were measured using a Fritsch Laser
Particle Sizer “Analysette 22”. The suspension of samples were
treated in ultrasonic bath before measurement for 60 s, and the
medium value of the particle size distribution (D50) was obtained
in mm.
The specific surface area of samples was determined by the BET
method via N2 adsorption at 77.3 K with a Micromeritics ASAP
2000 type equipment.
2.3.3. Compressive strength test
Compressive strength tests were performed according to EN
196-1 using a CONTROLS Automax5 equipment. The sample sur-
faces were polished even and parallel before testing. Three sam-
ples of each formulation were tested and the average data re-
ported at the age of 28 days. The loading rate was 5 71 kN/s for all
tests.
2.3.4. Thermogravimetric (TG) analysis
TG measurements were carried out on 400-mg portions of the
samples. The TG curves were recorded in a Derivatograph Q
1500D-type equipment (Hungarian Optical Works, Budapest) at a
heating rate of 10 °C/min, in static air atmosphere, using high-
grade corundum as the reference sample. The measurement was
performed in a temperature range of 25–1000 °C.
2.3.5. Fourier transform infrared (FTIR) spectroscopic analysis
The FTIR spectra of the samples were recorded in a Bruker
Vertex 70 spectrometer with a Platinum ATR adaptor, at a re-
solution of 2 cm  1 using a room-temperature DTGS detector. In
Please cite this article as: I. Balczár, et al., Mechanochemical and thermal activation of kaolin for manufacturing geopolymer mortars –
Comparative study, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.182i
I. Balczár et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 3
(001)
k k
k
q
mk k
q
k
m
m
DOA: 8 %
DOA: 70 %
DOA: 100 %
DOA: 100 %
15 20 25 30
Two theta (°)
each case 512 spectra were co-added. The reflectance spectra,
expressed as Kubelka-Munk units vs. wavenumber curves, were
very similar to absorbance spectra and were evaluated accordingly
with the OPUS software.
2.3.6. Scanning electron microscopy (SEM)
scanning electron microscope (Philips XL30 ESEM). Kaolin is in-
(1) trinsically non-conductive, therefore in high-vacuum mode the
samples were coated with gold/palladium films to a thickness of
2–3 nm using BALZERS SCD020 type equipment.
3. Results and discussion
3.1. XRD analysis
3.1.1. XRD analysis of TA kaolin samples
Endothermic dehydroxylation of kaolinite occurs at 550–
600 °C, which induces the change of a substantial fraction of the
surface Al from octahedral to tetrahedral coordination [17]. Tet-
rahedral coordination is favourable for geopolymerisation. Davi-
dovits was the first who investigated the structure of metakaolin-
based geopolymers, and had observed that during the course of
alkali-mediated reaction, Al(V) and Al(VI) in metakaolinite were
converted to tetrahedral sites with an associated alkali cation to
maintain electron neutrality [2].
Considering that dehydroxylation of Sedlec kaolin occurred
between 500 and 700 °C (Fig. 1), the heat-treatment temperatures
of 500 °C, 550 °C and 700 °C was applied. The main peak (7.2 Å) of
kaolinite was used to determine the progression of metakaolinite
formation. The reduced intensity of the main peak indicates the
transformation of kaolinite to metakaolinite.
The XRD patterns (Fig. 2) show the reduction (Fig. 2 curves
(b) and (c)) and disappearance (Fig. 2 curves (d) and (e)) of kao-
linite (k) peaks, and also appearance and increase of a wide
“amorphous” hump between 15° and 30° 2θ. The loss of intensity
and relative area in the main peak suggests the formation of
structurally disordered metakaolinite phase through release of
chemically bonded hydroxyl groups of kaolinite. Considering the
4 I. Balczár et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎

100 key grinding parameters for an effective mechanochemical acti-

vation which result in a high DOA value at the shortest possible
90 grinding time.
80 At first, the ms:mgb values were investigated using constant
500 rpm rotation speed and 15 min of grinding time (Fig. 4).
70
The XRD patterns of the MA kaolin samples show a reduction
DOA (%)

60
50
40
30
20
10
0
500 550
Heat-treatment temperature (°C)
Fig. 3. DOA of TA samples with 1 and 3 h of heat-treatment time.
results lower heat-treatment temperature as dehydroxylation
(569 °C) (curve (b)) is sufficient to begin the transformation of
kaolinite to metakaolinite, furthermore prolonged heat-treatment
time also facilitates the process (curve (c)). A one-hour long heat-
treatment at 700 °C is enough for complete transformation of
kaolinite to metakaolinite (curve (d)), but neither muscovite
(m) nor quartz (q) are altered during the process. Fig. 3 char-
acterises the rate of kaolinite to metakaolinite transformation. The
DOA value is seven times higher for the TA sample treated at
500 °C for 3 h than that for the TA sample treated at 500 °C for 1 h,
which also proves that a longer heat-treatment time at around the
starting of kaolinite dehydroxylation (at 500 °C) can result in sig-
nificantly higher rate of metakaolinite formation.
3.1.2. XRD analysis of MA kaolin samples
The XRD analysis of MA samples was applied because the
amorphisation process of kaolinite can easily be followed through
this investigation. The aim of this analysis was to determine the
and broadening of the main kaolinite peak (at 7.2 Å), and the ap-
pearance of an amorphous ring between 15° and 30° 2θ (Fig. 4),
which is related to the deformation and amorphisation of the
kaolinite structure [27]. The intensity of muscovite peaks
(m) reduces significantly indicating that the muscovite phase is
TA - 1 h also influenced by the mechanochemical activation in contrast to
the thermal activation, still quartz is not altered probably due to its
TA - 3 h higher hardness (its Mohs hardness is 7) [17]. The chosen ms: mgb
value was 1:11, because the DOA value does not change sig-
nificantly with further increase of the grinding body mass.
600 650 700 Rising of rotation speed considerably accelerated the degrada-
tion of kaolinite structure (Fig. 5). Using 500 rpm and 60 min
grinding time almost the same DOA value can be achieved as ap-
plying thermal activation at 700 °C and 1 h treatment time. (It
should be noted that while mechanochemical treatment actually
takes 60 min, the one-hour long thermal treatment time may be
extended to one day with 2.5 h of heating-up, and more than a half
day long cooling-down the furnace). However 600 rpm causes the
rapid warming-up of the zirconia bowl, thus the grinding process
had to be interrupted every 10 min. Consequently, the optimal
grinding parameters were found to be 500 rpm rotation speed,
1:11 mass ratio and 75 min grinding time.
3.2. Compressive strength of geopolymer mortars
Geopolymer specimens were produced using TA kaolin and MA
kaolin, each showing a DOA for more than 80%. The compressive
strength of geopolymer samples was determined at the 28th day
after casting.
In the case of thermal activation a strong correlation was dis-
covered between the DOA and compressive strength (Fig. 6), in-
creasing DOA value resulted in higher compressive strength.
Reaching the complete disappearance of the kaolinite main peak
(100% DOA value) also meant achieving the maximum strength

(001)
k k
Intensity (arbitrary unit)

k q
mk k
q
(a) m k
m

(b)
DOA: 57 %

(c)
DOA: 68 %

(d)
DOA: 72 %

5 10 15 20 25 30
Two theta (°)

Fig. 4. XRD patterns of untreated kaolin (a) and of MA samples using 500 rpm, and 15 min grinding time as well as (b) 1:8, (c) 1:11, and (d) 1:14 ms:mgb values. (k: kaolinite
PDF 14-164; m: muscovite PDF7-25; q: quartz PDF33-1161).

Please cite this article as: I. Balczár, et al., Mechanochemical and thermal activation of kaolin for manufacturing geopolymer mortars –
Comparative study, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.182i
 I. Balczár et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 5

100 60 100

Compressive Strength (MPa)

90
50
95 80
40 70
90 MA - 400 rpm

DOA (%)
60
30 MA - 500 rpm 50
85 MA - 600 rpm
DOA (%)

40
20 MA - 400 rpm 30
80 MA - 500 rpm
10 20
75 MA - 600 rpm 10
MA 400 rpm
0 0
70 MA - 500 rpm 0 40 80 120 160 200 240 280
Grinding time (min)
65 MA - 600 rpm
Fig. 7. Compressive strength (full symbol) of gepolymers derived from MA kaolin
60 samples and DOA (open symbol) of MA kaolin samples (using 400, 500, and
600 rpm rotation speed with 1:11 ms:mgb value).
0 40 80 120 160 200 240
Grinding time (min) the increase of rotation speed because of the higher agglomeration
of particles.
Fig. 5. DOA of MA samples using 400, 500, and 600 rpm rotation speed (with The highest strength value (55.6 MPa) was obtained by using
1:11 ms:mgb value). 400 rpm rotation speed and 4 h grinding time with 1:11 ms:mgb
value, which is significantly higher than 43.0 MPa obtained by
60 100 thermal activation. Mechanochemical activation, using 500 rpm
(75 min) or 600 rpm (80 min), led to similar compressive strength
Compressive Strength (MPa)

90
50 values as thermal activation.
80
According to Fitos et al. [28] the required energy for the ther-
40 70 mal activation of kaolinite is approximately 1600 kW h/t, while
DOA (%)

60 that for the mechanical activation is expected to be in the range of

30 50 200–1000 kW h/t in industrial environment. In the point of view
TA - 1 h 40 of cost-effectiveness, it seems to be a promising outcome of the
20 TA - 3 h present study, that mechanochemical activation does not require
30
longer treatment time than thermal activation under laboratory
TA - 1 h 20
10 conditions (which means that the required energy of thermal and
TA - 3 h 10 mechanical activation is comparable).
0 0
500 540 580 620 660 700 3.3. Specific surface area and particle size of TA and MA kaolin
Heat-treatment temperature (°C) samples

Fig. 6. Compressive strength (full symbol) of geopolymers derived from TA kaolins

Specific surface area (SSA) and medium value of the particle
and DOA (open symbol) of TA kaolin samples (using 1 and 3 h heat-treatment
time).
size distribution (D50-value) were determined on selected ther-
mally and mechanochemically activated kaolin samples, where the
highest compressive strength values were obtained on the tested
value (Fig. 6) with also noting that very small amounts of residual geopolymer mortars (Table 2). The main purpose of tests was to
crystalline phase can affect the mechanical strength significantly. investigate that not the enhanced specific surface area or the re-
Using the end temperature of dehydroxylation (700 °C) (Fig. 1), the duced particle size induced the reactivity of the kaolin.
compressive strength reached the highest value (43.0 MPa). The All activated samples had lower SSA value than the untreated
increased heat-treatment time, at 500 °C, causes greater DOA va- kaolin (19.4 m2/g) [29]. Thermal activation had a smaller impact
lue, which enhances the strength. But applying a 700 °C tem- on SSA value than mechanochemical one. Results also suggest that
perature the strength decreases slightly after longer heat-treat- SSA value of MA samples was greatly influenced by rotation speed
ment time, maybe because of the increased sintering of meta- (rising rotation speed decreased SSA value), while grinding time
kaolinite particles. had a smaller effect on SSA.
Geopolymer samples were also derived from MA kaolin sam- D50-value has some correlation with SSA. In every case D50-
ples with higher than 80% DOA values (the longest grinding time value of activated samples exceed that of the untreated kaolin
was much higher than the time necessary for total amorphisation). (6.6 mm), TA samples possess higher D50-value than MA samples,
In the case of each rotation speed used, the compressive strength
of the geopolymer mortar increases with grinding time and DOA Table 2
value up to 100% DOA value (Fig. 7). The maximum strength co- Specific surface area (SSA) and medium value of the particle size distribution (D50)
incides with the 100% DOA value. Further grinding causes slightly of untreated kaolin, MA and TA samples.
decreased strength, indicating that kaolin samples may lose re-
Sample Specific surface area (SSA) (m2/g) D50 (μm)
activity, because of the possible agglomeration of particles [16,17].
Increased rotation speed had a considerable effect on the degree of Untreated kaolin 19.4 6.6
amorphisation and it also strongly influenced compressive TA–700 °C/1 h 15.6 12.5
strength. Higher rotation speed can lead to the same DOA with a TA–700 °C/3 h 18.0 13.8
shorter grinding time, but the achieved strength (related to the MA–400 rpm/240 min 13.6 8.3
MA–500 rpm/75 min 12.3 9.6
same DOA value) decreases at higher rotation speeds, which in- MA–600 rpm/80 min 10.0 10.0
dicate that the reactivity of MA samples probably decreases with

Please cite this article as: I. Balczár, et al., Mechanochemical and thermal activation of kaolin for manufacturing geopolymer mortars –
Comparative study, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.182i
6 I. Balczár et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎

a even if TA samples have a larger SSA value. According to Juhász

0 (e) and Opoczky [30], the changes of MA samples in SSA and D50-
-2 (d) value can be used to identify the stage of grinding process, such as
-4 Rittinger section, aggregation section and agglomeration section.
(c)
Mass loss (wt%)

In the case of MA samples all SSA values decrease and all D50-
-6 values increase during the applied grinding, which corresponds to
-8 the agglomeration section of grinding process. To better under-
stand this phenomenon, SEM examinations were performed.
-10
(b)
-12 3.4. TG analysis of TA and MA kaolin samples
-14 (a)
Thermal analysis can provide useful information on the chan-
-16
ges of kaolinite structure upon different activations where XRD
-18 shows no difference. Seven different kaolin samples were selected
0 200 400 600 800 1000 for TG analysis, three mechanochemically activated, and four
thermally activated ones. In Fig. 8, the TG curve of the untreated
Temperature (°C) kaolin (a) shows two well-defined mass loss steps related to the
release of adsorbed water (at around 70 °C) and structural water of
b 0 kaolinite (at around 550 °C). For 1 h thermally activated samples
(a)
-2 the second defined mass loss step still remains, but with the in-
crease of temperature the amount of structural water decreases
-4
Mass loss (wt%)

(curves (b), (c) and (d)). This decrease of structural water corres-
-6 ponds to the XRD results, showing the reduction of crystallised
(f)
-8 kaolinite with the increase of temperature. Curve (e) shows that
after 3 h of thermal activation the whole structural water content
-10 vanishes.
-12 Fig. 8 reveals that mechanochemically activated samples
(curves (f), (g) and (h)) have a prolonged mass loss between 25
-14 (g)
and 600 °C. According to literatures [16,17], this prolonged mass
-16 (h) loss is attributed to the liberation of coordinated water formed as a
-18 result of mechanochemical activation. It also can be seen that the
0 200 400 600 800 1000 mass loss step of the liberation of structural water vanishes, which
corresponds to the 100% DOA value obtained by XRD analysis.
Temperature (°C)
3.5. FTIR spectroscopic analysis of TA and MA kaolin samples
Fig. 8. TG curves of (a) untreated kaolin, TA samples applying (b) 500 °C for 1 h,
(c) 550 °C for 1 h, (d) 700 °C for 1 h, (e) 700 °C for 3 h and MA samples using When kaolinites are treated either through mechanochemical
(f) 400 rpm for 240 min, (g) 500 rpm for 75 min and (h) 600 rpm for 80 min. or thermal activation, the structural changes can also be

Fig. 9. FTIR spectra of (a) untreated kaolin, TA samples applying (b) 500 °C for 1 h, (c) 550 °C for 1 h, (d) 700 °C for 1 h, (e) 700 °C for 3 h and MA samples using (f) 400 rpm
for 240 min, (g) 500 rpm for 75 min and (h) 600 rpm for 80 min.

Please cite this article as: I. Balczár, et al., Mechanochemical and thermal activation of kaolin for manufacturing geopolymer mortars –
Comparative study, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.182i
 I. Balczár et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 7

Fig. 10. SEM micrograph of (a) untreated kaolin, TA sample applying (b) 550 °C for 1 h, (c) 700 °C, for 1 h, and MA sample using (d) 400 rpm for 240 min, and (e) 500 rpm for
75 min.

characterised using FTIR spectra. Fig. 9 displays the changes due to
activations in kaolin samples at three different wavelength ranges.
The spectra of the untreated kaolin exhibited the following bands
of kaolinite: 3688, 3670, 3653 and 3620 cm  1 (O–H stretching
vibrations); 1024 cm  1 (Si–O stretching and bending vibrations);
997 and 460 cm  1 (Si–O vibrations); 927 and 910 cm  1 (AlVI–OH
bending vibrations); and 523 cm  1 (AlVI–O–Si bending vibrations)
[16–18,27].
In the case of TA samples (Fig. 9) the O–H stretching vibration
bands weaken with the rise of temperature (curves (b) and (c))
and disappear (corresponding to the given TG results) using heat-
treatment at 700 °C (curves (d) and (e)), showing no band in the
range of 2700–4000 cm  1.
Fig. 9 also represents that dry grinding of kaolinite destroys its
crystal structure by breaking O–H, Al–OH, Al–O–Si and Si–O bonds
[16]. The spectra of mechanochemically activated samples (curves
(f), (g) and (h)) exhibit neither of hydroxyl stretching bands at
3688, 3670, 3653, and 3620 cm  1 in addition to a broad band
around 3300 cm  1. This new band can be assigned to hydroxyl
stretching vibrations of coordinated and adsorbed water
[16,17,27]. The band changes in this area suggest that the co-
ordinated water (formed as a result of mechanochemical dehy-
droxylation) may cause the difference between mechanically and
thermally activated samples in reactivity and strength of mortar
samples. Water is one of the key parameters during geopolymer-
isation [2], and the weakly bonded water in the case of

Please cite this article as: I. Balczár, et al., Mechanochemical and thermal activation of kaolin for manufacturing geopolymer mortars –
Comparative study, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.182i
8 I. Balczár et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎
mechanochemical activation may better facilitate the sol-gel re-
action of geopolymerisation. To prove this theory further in-
vestigations are required.
The bands at 910 and 927 cm  1, associated to Al–OH bending
modes (of inner hydroxyls and inner surface hydroxyls, respec-
tively) [16,17,19], and the band at 523 cm  1 (assigned to AlVI–O–
Si) disappear after both of activation. A new band around
780 cm  1 appears in the spectra of thermally activated samples
and intensify with temperature (curves (c), (d) and (e)), which can
be assigned to AlIV–O vibration [27]. The reduction, broadening
and shifting to higher wavenumbers of Si–O bands (in spectra of
TA and MA kaolin samples) indicates the distortion of tetrahedral
and octahedral layers [16,17], it can be well observed in curves
(b) and (c) where Si–O bands become more and more similar to
the Si–O bands of sample treated at 700 °C with the increase of
temperature.
3.6. SEM analysis of TA and MA kaolin samples
The aim of SEM analysis was to supplement the examinations
of SSA and D50-value, and also better explain the obtained data.
SEM revealed that equally treated samples possessed similar
morphology. Fig. 10 shows that the platelet shape of kaolinite is
preserved in the case of TA samples even if the samples became
completely amorphous for XRD measurements (Fig. 10 (b) and (c)),
which also explains the higher specific surface area compared to
MA samples. Meanwhile, grinding significantly changes particle
shape; the mechanochemically activated samples have a highly
fragmented character, the particles become rounded, and also the
kaolinite plates are no more recognisable (Fig. 10 (d) and (e)). The
SEM images display that the mechanochemical activation leads to
the agglomeration of nanometre size spherical particles. The
shapeless compact agglomerates in turn lead to higher D50-value
and lower SSA, which corresponds well with the literatures
[17,27,31,32]. These agglomerates formed by mechanochemical
activation, according to Juhász and Opoczky [30], contain primary
particles, which are chemically bonded by irreversible adhesion. It
can be established, in agreement with the literatures [16–18,27,30–
32], TG, and FTIR results, that the success of mechanochemical
activation is primarily related to the destruction in the crystal
structure of kaolinite by the rupture of the O–H, Al–OH, Al–O–Si,
and Si–O bonds increasing surface energy and chemical reactivity.
According to SEM (Fig. 10 (d) and (e)) and particles size distribu-
tion analysis, the average size of the agglomerates is in the 8–
10 mm range, which contains primer particles with 100–200 nm
diameters. Comparing SEM micrograph (d), (e) and D50-values it
can be established that the agglomerates formed using 500 rpm
rotation speed are more compact than the agglomerates formed at
400 rpm. Considering strength results, the compactness of ag-
glomerates may influence negatively the geopolymerisation
process.
4. Conclusions
The results indicate that mechanochemical activation of kaoli-
nite can be a new and valuable method to manufacture geopoly-
mer binders in addition to the commonly used thermal activation.
Optimisation of the grinding process is a key issue to produce
geopolymer mortars with adequate strength, considering grinding
time, rotation speed, and ms: mgb value as variable parameters.
According to strength results, using mechanochemical activation
(1:11 mass ratio, 500 rpm rotation speed and 75 min grinding
time), 44.5 MPa compressive strength can be achieved, which is in
the same range as the best result (43.0 MPa) obtained by thermal
activation (applying 700 °C and 1 h heat treatment time).
Please cite this article as: I. Balczár, et al., Mechanochemical and thermal activation of kaolin for manufacturing geopolymer mortars –
Comparative study, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.182i
Furthermore, an increased heat-treatment time (3 h) resulted in
inferior reactivity and lower strength 32.3 MPa. The “degree of
amorphisation” (DOA) value also proved to be a useful indicator to
determine the degradation of the kaolinite structure and to predict
the reactivity of kaolin samples, but could not provide sufficient
information when the kaolinite became x-ray amorphous.
A number of fundamental structural differences were observed
between the thermally and mechanochemically activated samples.
Both activation methods could cause the complete demolition of
kaolinite structure within a one-hour treatment time, but thermal
activation does not alter the muscovite phase, while mechan-
ochemical activation also affected this constituent. Thermal acti-
vation primarily removes structural water, but also distorts the
tetrahedral and octahedral layers even if platelet shape of particles
remains, resulting a higher SSA and D50-value. On the other hand,
mechanochemical activation transforms the structural water of
kaolinite to a coordinated water, which may help later to form the
geopolymer-network. Mechanochemical activation also deeply
changes the morphology of kaolinite plates, forming compact ag-
glomerates (with the size of 8–10 mm) of nanometre size (100–
200 nm) rounded particles. It is suggested that this morphology of
MA samples also enhance the geopolymerisation reaction de-
pending on the compactness of agglomerates.
References
[1] H.H. Murray, W. Bundy, C. Harvey, Kaolin Genesis and Utilization, Specialist
Publication No. 1, The Clay Minerals Society, Boulder, CO, USA, 1993.
[2] J. Davidovits, Geopolymers: inorganic polymeric new materials, J. Therm. Anal.
37 (1991) 1633–1656.
[3] P. Duxson, A. Fernández-Jiménez, J.L. Provis, G.C. Lukey, A. Palomo, J.S.J. van
Deventer, Geopolymer technology: the current state of the art, J. Mater. Sci. 42
(2007) 2917–2933.
[4] H. Rahier, B. Van Mele, M. Biesemans, J. Wastiels, X. Wu, Low-temperature
synthesized aluminosilicate glasses. 1. Low-temperature reaction stoichio-
metry and structure of a model compound, J. Mater. Sci. 31 (1) (1996) 71–79.
[5] A. Palomo, M.T. Blanco-Varela, M.L. Granizo, F. Puertas, T. Vazquez, M.
W. Grutzeck, Chemical stability of cementitious materials based on meta-
kaolin, Cem. Concr. Res. 29 (7) (1999) 997–1004.
[6] A. Elimbi, K.H. Tchakoute, D. Njopwouo, Effects of calcination temperature of
kaolinite clays on the properties of geopolymer cements, Constr. Build. Mater.
25 (2011) 2805–2812.
[7] A.M. Rashad, Metakaolin as cementitious material: history, scours, production
and composition — a comprehensive overview, Constr. Build. Mater. 41 (2013)
303–318.
[8] Ch Bich, J. Ambroise, J. Péra, Influence of degree of dehydroxylation on the
pozzolanic activity of metakaolin, J. Appl. Clay Sci. 44 (2009) 194–200.
[9] Z. Zhang, H. Wang, X. Yao, Y. Zhu, Effects of halloysite in kaolin on the for-
mation and properties of geopolymers, Cem. Concr. Compos. 34 (2012)
709–715.
[10] F. Zibouche, H. Kerdjoudj, J.-B. de Lacaillerie, H. Van Damme, Geopolymers
from Algerian metakaolin: influence of secondary minerals, Appl. Clay Sci. 43
(2009) 453–458.
[11] Z. Zuhua, Y. Xiao, Z. Huajun, C. Yue, Role of water in the synthesis of calcined
kaolin-based geopolymer, Appl. Clay Sci. 43 (2009) 218–223.
[12] A. Autef, E. Joussein, G. Gasgnier, S. Pronier, I. Sobrados, J. Sanz, S. Rossignol,
Role of metakaolin dehydroxylation in geopolymer synthesis, Powder Technol.
250 (2013) 33–39.
[13] M.R. Wang, D.C. Jia, P.G. He, Y. Zhou, Influence of calcination temperature of
kaolin on the structure and properties of final geopolymer, Mater. Lett. 64
(2010) 2551–2554.
[14] R. Cioffia, L. Maffucci, L. Santoro, Optimization of geopolymer synthesis by
calcination and polycondensation of a kaolinitic residue, Resour. Conserv.
Recycl. 40 (2003) 27–38.
[15] R.M. Torres Sánchez, E.I. Basaldella, J.F. Marco, The effect of thermal and me-
chanical treatments on kaolinite: characterization by XPS and IEP measure-
ments, J. Colloid Interface Sci. 215 (1999) 339–344.
[16] R.L. Frost, É. Makó, J. Kristóf, E. Horváth, J.T. Kloprogge, Mechanochemical
treatment of kaolinite, J. Colloid Interface Sci. 239 (2001) 458–466.
[17] É. Makó, R.L. Frost, J. Kristóf, E. Horváth, The effect of quartz content on the
mechanochemical activation of kaolinite, J. Colloid Interface Sci. 244 (2001)
359–364.
[18] C. Vizcayno, R.M. de Gutiérrez, R. Castello, E. Rodriguez, C.E. Guerrero, Poz-
zolan obtained by mechanochemical and thermal treatments of kaolin, Appl.
Clay Sci. 49 (2010) 405–413.
[19] S. Kumar, R. Kumar, Mechanical activation of fly ash: Effect on reaction,
 I. Balczár et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 9

structure and properties of resulting geopolymer, Ceram. Int. 37 (2011)
533–541.
[20] G. Mucsi, S. Kumar, B. Csőke, R. Kumar, Z. Molnár, Á. Rácz, F. Mádai, Á. Deb-
reczeni, Control of geopolymer properties by grinding of land filled fly ash, Int.
J. Miner. Process. 143 (2015) 50–58.
[21] J. Temuujin, R.P. Williams, A. van Riessen, Effect of mechanical activation of fly
ash on the properties of geopolymer cured at ambient temperature, J. Mater.
Process. Technol. 209 (2009) 5276–5280.
[22] D.N. Hinckley, in: Clays & Clay Minerals, Proceedings of 11th Natural Con-
ference, Pergamon, Oxford, 1963, p. 229.
[23] P. Duxson, J.L. Provis, G.C. Lukey, S.W. Mallicoat, W.M. Kriven, J.S.J. van De-
venter, Understanding the relationship between geopolymer composition,
microstructure and mechanical properties, Colloid Surf. A 269 (2005) 47–58.
[24] P. Duxson, S.W. Mallicoat, G.C. Lukey, W.M. Kriven, J.S.J. van Deventer, The
effect of alkali and Si/Al ratio on the development of mechanical properties of
metakaolin-based geopolymers, Colloid Surf. A 292 (2007) 8–20.
[25] I. Balczár, T. Korim, A. Dobrádi, Correlation of strength to apparent porosity of
geopolymers – understanding through variations of setting time, Constr. Build.
Mater. 93 (2015) 983–988.
[26] F.G.M. Aredes, T.M.B. Campos, J.P.B. Machado, K.K. Sakane, G.P. Thim, D.
D. Brunelli, Effect of cure temperature on the formation of metakaolinite-
based geopolymer, Ceram. Int. 41 (2015) 7302–7311.
[27] É. Makó, Zs Senkár, J. Kristóf, V. Vágvölgyi, Surface modification of mechan-
ochemically activated kaolinites by selective leaching, J. Colloid Interface Sci.
294 (2006) 362–370.
[28] M. Fitos, E.G. Badogiannis, S.G. Tsivilis, M. Perraki, Pozzolanic activity of
thermally and mechanically treated kaolins of hydrothermal origin, Appl. Clay
Sci. 116–117 (2015) 182–192.
[29] N. Vdović, I. Jurina, S.D. Škapin, I. Sondi, The surface properties of clay mi-
nerals modified by intensive dry milling — revisited, Appl. Clay Sci. 48 (2010)
575–580.
[30] A.Z. Juhász, L. Opoczky, Mechanical Activation of Minerals by Grinding: Pul-
verizing and Morphology of Particles, Academic Press, Budapest, 1990.
[31] É. Kristóf, A.Z. Juhász, I. Vassányi, The effect of mechanical treatment on the
crystal structure and thermal behaviour of kaolinite, Clays Clay Miner. 41 (5)
(1993) 608–612.
[32] E.F. Aglietti, J.M. Porto Lopez, E. Pereira, Mechanochemical effects in kaolinite
grinding. I. Textural and physicochemical aspects, Int. J. Miner. Process. 16
(1986) 125–133.

Please cite this article as: I. Balczár, et al., Mechanochemical and thermal activation of kaolin for manufacturing geopolymer mortars –
Comparative study, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.182i