Construction and Building Materials 188 (2018) 924–933

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Construction and Building Materials

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Rheological properties and microstructure of binary waste red brick

powder/metakaolin geopolymer
Pavel Rovnaník a,⇑, Pavla Rovnaníková a, Martin Vyšvařil a, Stefania Grzeszczyk b,
_
Elzbieta Janowska-Renkas b
a
Faculty of Civil Engineering, Brno University of Technology, Veveří 95, 602 00 Brno, Czech Republic
b
Faculty of Civil Engineering and Architecture, Opole University of Technology, Katowicka 48, 45-061 Opole, Poland

h i g h l i g h t s

Addition of waste red brick powder causes a decrease in plastic viscosity of metakaolin-based geopolymer.

Thixotropic behavior of metakaolin diminished when more than 75% of waste red brick powder was used in geopolymer mixture.

Part of the crystalline phase in waste red brick takes part in the geopolymerization process.

Waste red brick powder and metakaolin show a synergic effect on the compressive strength of blended geopolymer.

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

Article history: Waste brick powder is a material with sufficient pozzolanic properties to be used as a supplementary
Received 13 July 2018 cementing material in Portland cement-based concrete or as a precursor for the production of geopoly-
Received in revised form 22 August 2018 mers. This study aimed to investigate a binary geopolymer system composed of metakaolin (MK), waste
Accepted 23 August 2018
red brick (WRB) powder and sodium silicate solution as an alkaline activator. Five different mixtures
were prepared where 0, 25, 50, 75, and 100% of the MK was substituted with WRB. The rheological
parameters of the fresh pastes were correlated with a structural evaluation of the reaction process.
Keywords:
The findings showed that the yield stress of all mixtures was very low, but it increased with time as the
Waste brick powder
Metakaolin
geopolymerization reaction proceeded. The more MK was used in the mixture, the faster the yield stress
Geopolymer developed. On the other hand, the plastic viscosity strongly depended on the composition of the mixtures
Rheology and dropped with increasing WRB/MK ratio. The mixtures containing more than 50% MK exhibited a
Mechanical properties decrease in viscosity with time due to higher reactivity and the faster dissolution of the MK particles.
IR spectroscopy Ó 2018 Elsevier Ltd. All rights reserved.
NMR spectroscopy

1. Introduction significant amount of waste ceramic dust which is mostly land-

Ceramic waste is generated all over the world in large quantities.
The ceramic industry itself widely contributes to its production in
the form of scrap. For instance, in Europe, the amount of waste pro-
duced in the different production stages of the ceramic industry
reaches 3–7% of global production [1]. Current trends in the build-
ing sector are for the utilization of thin-joint technology in the con-
struction of building envelopes. Since current hollow brick
production techniques do not provide sufficiently smooth and even
surfaces, the brick blocks have to be surface ground, generating a
⇑ Corresponding author.
E-mail addresses: rovnanik.p@vutbr.cz (P. Rovnaník), rovnanikova.p@fce.vutbr.
cz (P. Rovnaníková), vysvaril.m@fce.vutbr.cz (M. Vyšvařil), s.grzeszczyk@po.edu.pl
(S. Grzeszczyk), e.janowska-renkas@po.opole.pl (E. Janowska-Renkas).
filled, although it has both the composition and granulometry
needed to be suitable for application in the building industry.
Waste red brick (WRB) powder is a material with pozzolanic
properties. Pozzolanicity is dependent on several characteristics,
of which the main ones are the amount of amorphous phase, par-
ticle size distribution, and specific surface area. The pozzolanicity
of burned clays was determined by Baronio and Binda [2] in
1997. The authors concluded that pozzolanic properties are depen-
dent on the temperature and burning time of the brick body. Böke
et al. [3] determined the pozzolanic activity of brick aggregate in
old mortars and plasters via electrical conductivity measurements
and showed that pozzolanic properties are consistent with amor-
phous phase content. Pozzolanic activity allows the use of WRB
powder as a supplementary cementing material in concrete [4,5],
an application which has been known since antiquity in Rome,

https://doi.org/10.1016/j.conbuildmat.2018.08.150
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
 P. Rovnaník et al. / Construction and Building Materials 188 (2018) 924–933 925

Greece and Mesopotamia. It also enables such powder to be
employed as a component of modified lime mortars and plasters,
in which manner it has been used since the Middle Ages [6–8].
WRB powder can be successfully used as a precursor in alkali-
activated materials or geopolymers [9]. These are generally com-
posed of aluminosilicates with specific properties and an alkaline
solution as an activator. Waste-based materials and by-products
used in building industry are considered to be environmentally
friendly, hence common aluminosilicate precursors are fly ashes
from power plants, palm oil fuel ash, ash from biomass, slag, waste
brick powder, waste glass, stone dust, incineration products of
sludges, and similar materials containing amorphous silica and/or
aluminosilicates [10]. Another precursor utilized for geopolymer
production is metakaolin (MK), which is manufactured by the cal-
cination of kaolinite containing rocks at 750 °C [11,12]. Since its
production is quite expensive, energy consuming process with
strong environmental impact, WRB powder can be used as a rea-
sonable alternative to this material.
The course of the alkaline activation of WRB powder is influ-
enced by several factors: the amorphous phase content, particle
size, the composition and dosage of the alkaline activator, and tem-
perature. The amorphous phase content is associated with the
composition of the raw material for brick making and the burning
temperature. These parameters are given and cannot be influ-
enced; therefore, it is necessary to determine the pozzolanic activ-
ity of the WRB powder and the amorphous phase content by means
of quantitative XRD analysis. The pozzolanic activity determined
by the Chapelle test is given in mg of Ca(OH)2 per 1 g of pozzolan
and ranges from 300 to 500 mg Ca(OH)2 for common RB powders
[13].
The composition and amount of alkaline solution play an
important role during the formation of geopolymer products.
Sodium/potassium silicate solution modified by sodium/potassium
hydroxide is the most commonly used alkaline activator. The effect
of the amount and composition of alkaline activator has been
investigated by several authors. Tuyan et al. [14] found the opti-
mum activator composition had SiO2/Na2O = 1.6 and a concentra-
tion of 10% Na2O. Maximum compressive strength was obtained
upon curing at 90 °C for 5 days, but in terms of energy consump-
tion, the optimum treatment was at 80 °C for 5 days. Similar
results were also obtained by Reig et al. [15], who studied the
geopolymerization of WRB powder at a constant water/binder
ratio and a curing temperature of 65 °C.
The above-mentioned studies indicate that WRB powder is
mostly activated at higher temperatures, usually above 60 °C, in
order to attain sufficient mechanical properties. For this reason,
it is preferred to use WRB powder in a blend with other reactive
material, e.g. metakaolin, fly ash or slag, in order to maintain effec-
tive curing under laboratory conditions. Rakhimova [16] investi-
gated the effect of the addition of waste brick powder in various
amounts, with a variety of compositions and from different sources
on the properties of pastes and mortars made of alkali-activated
slag. Mixtures where 20 and 40% of the slag was replaced by waste
brick reached the highest compressive strength (in the range of
compared the yield stress for mixtures made from Portland
cement, alkali-activated blast furnace slag and fly ash with various
liquid/binder ratios and found that the workability of alkali-
activated binders is more sensitive to changes in the composition
of the mixture than Portland cement. Favier et al. [19,20] reported
that the low yield stress of MK-based geopolymer compared to
Portland cement paste is caused by negligible and only low energy
interactions between MK grains. The high viscosity of MK-based
mixture is then caused by hydrodynamic viscous dissipation in
the highly viscous sodium silicate solution. Poulesquen [21] stud-
ied mixtures of metakaolin and alkaline activator prepared from
two types of amorphous silica (Tixosil 331 or Aerosil) and
sodium/potassium hydroxide. The viscoelastic parameters of vari-
ous geopolymers were evaluated using dynamic rheology and
showed there is a relation between the formation and size of oligo-
mers and the type of alkaline solution. The authors found faster
geopolymerization kinetics with sodium hydroxide but with
weaker interaction between components, and hence the limited
formation of oligomers, whereas potassium alkaline solution
preferably formed a three-dimensional structure.
The present study deals with the properties of fresh mix and
hardened geopolymers prepared from metakaolin, WRB powder
and modified sodium silicate solution. Rheological properties such
as the plastic viscosity and yield stress of fresh mixes were deter-
mined and the dissolution/reaction process was evaluated using
XRD, FTIR and NMR analysis.
2. Materials and sample preparation
Geopolymer mixtures were prepared from MK and WRB pow-
der as aluminosilicate precursors, and modified sodium water glass
was used as an alkaline activator. The metakaolin was supplied by
ČLUZ company, Czech Republic. The red brick powder was a waste
material obtained from the grinding of hollow red-clay bricks from
Heluz company. The activating solution was prepared by mixing
1000 g of commercial sodium water glass with an SiO2/Na2O ratio
of 1.6 and 37 g of NaOH p.a. in order to adjust the SiO2/Na2O value
to 1.4. The chemical composition of both the aluminosilicates and
the water glass is presented in Table 1.
The particle size distribution of both aluminosilicate precursors
was determined by laser granulometry measurement and the dis-
tribution curves are presented in Fig. 1. The mean particle size of
the WRB powder (d50 = 8.5 mm) was very similar to that of the
MK (d50 = 6.3 mm). However, the WRB powder exhibited a much
wider range of particle size than metakaolin. The d90 value, which
indicates that 90% of all grains are smaller than a given value, was
56.5 mm for the WRB, whereas it was only 11.6 mm for the MK.
Rheological properties were determined for the pastes, which
were composed of 40 g of aluminosilicate precursor, 36 g of alka-
line activator and 20 mL of water. The composition of the alumi-
Table 1
Chemical composition of metakaolin, red brick powder and water glass (wt%).

90–120 MPa), and the reaction rate dramatically decreased with Component Metakaolin Red brick Water
the increasing specific surface area of the brick powder. powder glass
Only few research works concerning the rheology of fresh SiO2 58.70 52.37 26.43
geopolymer mixtures have been published so far. The rheological Al2O3 38.50 12.50 –
properties of geopolymers depend on several factors and cannot Fe2O3 0.72 2.41 –
CaO 0.20 22.83 –
be easily generalized as this group of materials involves several dif-
MgO 0.38 1.44 –
ferent types of aluminosilicate precursors as well as various alka- Na2O 0.04 0.24 16.61
line activator types and concentrations. Kashani at al. [17] K2O 0.85 2.46 –
reported that the use of alkali hydroxide causes a significant SO3 0.02 3.71 –
increase in the yield stress of an activated slag paste, whereas TiO2 0.49 0.40 –
LOI 1.67 0.00 –
sodium silicate gives a lower yield stress due to the plasticizing Pozzolanic activity (mg Ca(OH)2/g) 1120 467 –
and deflocculating effects of the silicate ions. Alonso et al. [18]
926 P. Rovnaník et al. / Construction and Building Materials 188 (2018) 924–933
Fig. 1. Particle size distributions of WRB powder and metakaolin determined by laser granulometry measurement.
nosilicate precursor varied between pure brick powder (MK0) and
pure metakaolin (MK100), which were used for two of the mix-
tures. In the other mixtures, 25, 50, and 75% of the brick powder
was replaced by metakaolin. The samples are labelled according
to the percentage of metakaolin in the sample, i.e. sample MK25
contains 25% metakaolin and 75% brick powder. The specimens
prepared for the mechanical testing were cast in prismatic moulds
(20  20  100 mm) and sealed with PE foil. The fresh mixtures
were first stored for 4 h at ambient temperature and then cured
for 20 h at 40 °C in an electric oven. After this period, the hardened
specimens were demoulded and stored in plastic bags under labo-
ratory conditions.
The course of the reaction was monitored during the first
180 min by means of Fourier-transform infrared spectroscopy
(FTIR) and solid-state nuclear magnetic resonance (NMR). In order
to analyse the structure of intermediates and early products, the
geopolymerization reaction was stopped at the age of 60, 120,
and 180 min using a simplified method published by Chen et al.
[22]. 80 mL of solvent (methanol/acetone (1:1 vol) mixture) was
added to 1.0 g of geopolymer paste and the resulting suspension
ground with a pestle so that all particles would come into contact
with the solvent. After that, the suspension was stirred for 5 min
using a magnetic stirrer and then the solvent was removed by vac-
uum filtration. This procedure was repeated three times. Finally,
the sample was washed twice with 10 mL of diethyl ether.
3. Experimental methods
Characterizations of the particle size distribution were carried
out by means of a Malvern Mastersizer 2000 laser particle analyzer
using an aqueous suspension. The pozzolanic activity of the WRB
and MK was determined via a modified Chapelle test. The Chapelle
test consisted in heating a sample of pozzolan with freshly
annealed lime and water in a tightly closed container at a temper-
ature of 93 °C for 24 h. The mixture was stirred with a magnetic
stirrer. The residual calcium hydroxide was determined by titra-
tion with a standard solution of hydrochloric acid in the presence
of sucrose. The results are expressed in the mg of Ca(OH)2 which
are consumed in the reaction with 1 g of pozzolan per 24 h [13].
Rheological measurements of the pastes were performed by
means of a Discovery HR-1 (TA Instruments) hybrid rheometer
and TRIOS 4.0.2.30774 software was used for data evaluation.
The measurements were performed in a Peltier Concentric Cylinder
system with a DIN rotor at 25 °C. The standard gap for the DIN
cylinder system (5.917 mm) was employed. The paste was intro-
duced into the measurement system at the end of the mixing cycle.
The rheological measurements were started after a period of rest of
60 s. Paste properties were estimated from the flow curves deter-
mined for increasing and decreasing values within the shear stress
range from 0.1 to 100 s1. The measurement was repeated at 20,
40, 60, 80, 100, 120, 180, and 240 min. Yield stress values and plas-
tic viscosities were determined from the decreasing branch of the
flow curve using the Bingham model [23]. The time evolutions of
the viscoelastic properties of the pastes were evaluated by small
amplitude (0.01%) oscillation tests at the 1 Hz frequency. Before
such measurements, it is important to determine the linear vis-
coelasticity region (LVR) in order to prevent structural decomposi-
tion of the geopolymerized network. The LVR is the region in which
measurements are nondestructive to the microstructure of a mate-
rial, and it ends at a critical strain, cc. The strain of 0.01% used in
the oscillation tests was lower than the critical strain for all pastes
studied.
X-ray powder diffraction analysis and the determination of the
amorphous phase were carried out on a Panalytical Empyrean
diffractometer equipped with a Cu tube (kKa = 0.15406 nm). The
diffraction pattern was collected from 5° to 80° with a step size
of 0.013° and a time per step of 150 s. The quantitative phase anal-
ysis was performed according to the Rietveld method using the
fundamental parameters approach with CaF2 as an internal stan-
dard. The data were processed using HighScore + software and
the ICDD PDF 2 and ICSD 2012 databases. Fourier transform infra-
red (FTIR) spectra of the finely ground samples were collected
using a Perkin Elmer FrontierTM spectrometer equipped with a sin-
gle reflectance ATR attachment using diamond crystal. The FTIR
spectra were collected in the absorbance mode from 520 to
4000 cm1 at a resolution of 2 cm1 and 64 scans per spectrum.
Solid-state NMR spectra were recorded on a Bruker Avance III HD
700 MHz spectrometer equipped with a double-resonance 4-mm
MAS DVT 700S4 BL4 N-P/H. The resonance frequency for 27Al
was 182.61 MHz. Spectra were recorded via MAS techniques, with
a sample spinning rate of 10 kHz. The number of scans was 300 and
the 27Al chemical shift is quoted relative to external 1 M aluminum
nitrate solution. A JEOL JSM 840 scanning electron microscope in
secondary electron imaging mode was used for the microstructural
characterisation of metakaolin particles.
Mechanical properties were tested using prismatic specimens
with dimensions of 20  20  100 mm at the age of 7 and 14 days.
Flexural strengths were determined using a standard three-point-
bending test and compressive strengths were measured on the far
edge of each of the two residual pieces obtained from the flexural
test according to the EN 196-1 standard. For each mixture, a set of
three specimens was used.

4. Results and discussion
4.1. Mechanical properties
The compressive and flexural strengths of the geopolymer mix-
tures with various WRB/MK ratios are presented in Fig. 2. The tests
were performed at two different geopolymer paste ages, 7 and
14 days. The lowest 7-day compressive strength (10.2 MPa) was
achieved for the mixture where only WRB powder was used as
an aluminosilicate precursor. When the WRB powder was replaced
by MK, the strength linearly increased as more MK was used. How-
ever, the pure MK-based geopolymer again showed slightly
decreased values with respect to the MK75 mixture. This suggest
a kind of synergistic effect of MK and WRB powder on the mechan-
ical properties of geopolymer. Similiar synergy was also reported
for the concrete made of Portland cement and two and more differ-
ent types of mineral admixtures [24,25]. The increase in compres-
sive strength of 3.2–4.5 MPa between the age of 7 and 14 days was
only observed for the mixtures with WRB powder. Since there was
practically no difference between the 7 and 14-day strengths of
MK-based geopolymer, it suggests WRB undergoes a slightly
slower reaction. The flexural strength followed the same trend as
that observed for compressive strength with a minimum of
0.78 MPa for pure WRB-based geopolymer and a maximum of
4.50 MPa for the MK75 mixture.
4.2. Rheological properties
For the rheological testing, geopolymer pastes with various
WRB/MK ratios were prepared; the results are presented in Figs. 3–
5, and in Table 2. The curves in Fig. 3 indicate the strong thixotropic
behaviour of the pure MK-based geopolymer. As the MK content
decreased, the thixotropic effect diminished, and no thixotrophy
was observed for the MK0 and MK25 mixtures. During the first
60 min, mitigation of the thixotropic behaviour was observed for
the blended geopolymer mixtures (MK50 and MK75); however,
practically no changes occurred for the pure MK-based geopolymer
(MK100).
As the position of flow curves (Fig. 3) and the data presented in
Table 2 show, the highest plastic viscosity in the initial period
(after 5 min) was demonstrated by the sample of geopolymer with
pure metakaolin (MK100) – gpl = 2.18 Pa s. In this case, a slight
yield stress value was also observed (s0 = 1.65 Pa). This increased
with time, and after 240 min of testing it reached 16.05 Pa
(Fig. 5, Table 2). On the other hand, the lowest rheological param-
eters, with regard to both the plastic viscosity and the yield stress,
were observed for the geopolymer with pure red brick powder over
the entire measurement period (from 5 to 240 min). As with the
pure MK-based geopolymer, an increase in plastic viscosity was
observed over time, but to a much lower extent. As a result,
35
7d
Compressive strength (MPa)
30
14 d
25
20
15
10
0
MK0 MK25
Fig. 2. Compressive (left) and flexural (right) strengths of geopolymer mixtures determined at the age of 7 and 14 days.
P. Rovnaník et al. / Construction and Building Materials 188 (2018) 924–933 927
5 min after mixing the plastic viscosity was only 0.09 Pa s; after
240 min it had risen to 0.23 Pa s. The very low yield stress values
ranging from 0.04 Pa (after 5 min) to 1.08 Pa (after 240 min) indi-
cate that this geopolymer shows the properties of a Newtonian
fluid.
The replacement of the metakaolin in the pure MK-based
geopolymer with WRB in quantities ranging from 25 to 75% by
mass causes a gradual reduction in plastic viscosity with higher
brick powder content in the mixture. Taking into account the yield
stress value of the tested samples (Fig. 2a–d), it can be stated that
these samples demonstrate properties close to those of Newtonian
fluids with very low yield stress. It can be noticed, however, that in
the samples where WRB powder was 25–75% by mass of the total
precursor content, the yield stress gradually decreased with rising
WRB content, being 8.75 Pa and 0.08 Pa for the geopolymer sam-
ples containing 25% and 75% WRB powder by mass, respectively.
In general, the yield stress of the tested geopolymers is very low
whereas the plastic viscosity increases with decreasing WRB/MK
ratio.
The analysis of the plastic viscosity for tested samples of
geopolymers over time from 5 to 240 min (Figs. 3 and 4) demon-
strated that with increasing time the plastic viscosity of samples
with more than 50% of metakaolin reduced, whereas it did not
change for the MK25 and MK0 mixtures. The highest reduction
in viscosity took place in the initial period of time of up to
60 min, but in the period stretching from 120 to 240 min the plas-
tic viscosity remained more or less at the same level. During the
same period, the geopolymers containing the largest quantity of
WRB powder, MK25 and MK0, showed a slight increase in plastic
viscosity from 0.17 Pa s to 0.22 Pa s, and from 0.10 Pa s to
0.23 Pa s, respectively.
The time evolution of the viscoelastic properties of the geopoly-
mer mixtures was evaluated by small amplitude (0.01%) oscillation
tests at a frequency of 1 Hz measuring the dynamic moduli, G0 and
G00 , which represent the elastic and viscous behaviour of a material.
If the elastic behaviour dominates the viscous behaviour (G0 > G00 ),
the sample exhibits a certain rigidity. Conversely, if G00 > G0 , the
sample shows the character of a liquid without a consistent chem-
ical or physical network-of-forces. Experimental data were also
reported in terms of loss factor, tan d, defined by Eq. (1).
00 0
tan d ¼ G =G ð1Þ
Viscoelastic materials such as fresh geopolymer pastes react to
strain with a temporal delay, which is expressed by the phase shift
angle (or loss angle) d, or the loss factor tan d. The loss factor is cal-
culated as the quotient of the lost and stored deformation energy.
Therefore, it reveals the ratio between the viscous and the elastic
part of the deformation behaviour (0  tan d  1). Purely elastic
materials are indicated by tan d = 0 and ideal viscous behaviour
might be expressed as tan d = 1.
MK50 MK75 MK100
928 P. Rovnaník et al. / Construction and Building Materials 188 (2018) 924–933

(a) (b)

(c) (d)
Fig. 3. Flow curves of geopolymer mixtures with various WRB/MK ratios: a) after 5 min, b) after 60 min, c) after 120 min; d) after 180 min.

Fig. 4. Changes in the plastic viscosity of geopolymers over time. Fig. 5. Changes in the yield stress of geopolymers over time.
 P. Rovnaník et al. / Construction and Building Materials 188 (2018) 924–933 929

Table 2
Plastic viscosity and yield stress of geopolymers determined after 5–240 min.

Mixture Time (min) Viscosity (Pa s) Yield stress (Pa)

MK0 5 0.09 0.04
20 0.09 0.03
40 0.09 0.04
60 0.10 0.06
80 0.10 0.08
100 0.10 0.11
120 0.11 0.14
180 0.15 0.25
240 0.23 1.08
MK25 5 0.19 0.08
20 0.18 0.12
40 0.17 0.16
60 0.17 0.20
80 0.17 0.26
Fig. 6. Time evolution of the storage modulus (G0 ) and loss modulus (G00 ) of
100 0.18 0.33
geopolymer mixtures.
120 0.18 0.50
180 0.19 0.95
240 0.22 2.11
MK50 5 0.64 0.00
20 0.56 0.22
40 0.52 0.47
60 0.50 0.67
80 0.48 0.88
100 0.47 1.12
120 0.46 1.35
180 0.47 3.14
240 0.49 5.52
MK75 5 1.76 0.03
20 1.26 1.06
40 1.18 1.42
60 1.11 1.82
80 1.05 2.32
100 1.01 2.78
120 0.97 3.06
180 0.97 5.91
240 0.95 8.75
Fig. 7. Time evolution of the loss factor of geopolymer mixtures.
MK100 5 2.18 0.00
20 1.99 0.55
40 1.84 1.72
sition of the aluminosilicate precursors, MK and WRB powder,
60 1.73 2.96
80 1.64 4.66 and MK0 mixture at the age of 180 min was determined by XRD
100 1.60 6.14 analysis (Fig. 8). The Rietveld method was used in order to evaluate
120 1.55 7.38 the relative quantities of the determined phases, employing the
180 1.59 11.86 fundamental parameters approach in combination with the CaF2
240 1.57 16.05
internal standard. The results of the quantitative analysis are pre-
sented in Table 3.
The MK precursor consisted predominantly of amorphous
Fig. 6 shows the time evolution of viscoelastic parameters (G0
phase, of which only 15% was composed of crystalline impurities
and G00 ) during a geopolymerization test. The elastic modulus
comprising mainly quartz with traces of corundum, mica, and
quickly exceeded the viscous modulus in mixtures with 50% and
anatase. On the other hand, up to 78% of the WRB powder was
more MK, indicating the existence of interactions between the con-
crystalline matter, which comprised quartz, mica, anorthite, ortho-
stituents and a predominance of gel or solid properties in the
clase, and traces of hematite, gehlenite and calcite. Analysis
materials even before setting. The mixtures with below 50% MK
of the MK0 mixture was performed to determine whether any
initially showed the character of a liquid, but the existence of a
crystalline species in WRB take part in the geopolymerization pro-
crossover point, G0 = G00 (gel point), implies the formation of a gel
cess. The quantitative analysis showed that the amorphous phase
network over time. It is evident that the reaction kinetics of the
increased by approx. 40% compared to pure WRB powder, and
MK-based geopolymer are much faster than those of the WRB-
the highest decrease in intensity was observed for mica type
based geopolymer. The time evolution of the loss factor (Fig. 7)
mineral.
confirmed the prevalence of the elastic part of the deformation
energy and the gel-like behaviour of pastes with 50% and more
MK. Loss factor values decreased over time, indicating the gradual
4.4. Fourier transform infrared analysis
gelation of the microstructure of pastes.
The FTIR spectra of the prepared geopolymer mixtures were
4.3. XRD analysis analysed mainly for the asymmetric stretching vibration of
SiAOAT linkages (T@Si or Al), which are represented by the point
Since the microstructure of a blended mixture is usually a of maximum absorbance in the region 1300–900 cm1 (‘‘main
superposition of pure components, the microstructural analysis band”) [26]. Absorption features in the inspected region of the
was mainly focused on the reaction process of pure MK-based spectra are broadened and asymmetric and imply the overlap of
and WRB-based geopolymer mixtures. The mineral phase compo- more bands (Fig. 9). The FTIR spectrum of the MK precursor is rep-
930 P. Rovnaník et al. / Construction and Building Materials 188 (2018) 924–933

There are several other features in the spectra but these are not
associated with changes in aluminosilicate structure. The band at
1650 cm1 is associated with the bending mode of absorbed H2O
molecules. The bands at 1445 and 1437 cm1 can be attributed
to the stretching of different carbonate species, while the band at
881 cm1 represents their bending mode [30]. Their formation is
caused by the carbonation reaction of alkalis with atmospheric
CO2 during the storage of the samples before FTIR measurement.
Although the samples were stored in closed plastic vessels this
process is difficult to prevent. However, it is interesting that the
carbonation level is much higher in the case of WRB-based
geopolymer.

27
4.5. Al MAS NMR analysis

The spectra of the time evolution of MK-based and WRB-based

geopolymer are presented in Figs. 11 and 12, respectively. The
spectrum for MK contains signals indicating the presence of octa-
hedral (chemical shift 3.7 and 14.3 ppm) and pentahedral
(28.4 ppm) Al [31,32]. After activation, a strong peak appeared at
58.3 ppm within the first 60 min. This peak is associated with
tetrahedral Al coordinated with four Si, which has been reported
to be the main coordination type in geopolymer structure [33].
The small peak or shoulder in the chemical shift at 70 ppm can
Fig. 8. X-ray patterns of A) metakaolin; B) red brick; C) MK0 mixture at the age of be attributed to not fully condensed AlO4 tetrahedra corresponding
180 min. The spectra contain peaks of CaF2, which was used as an internal standard to Al(2OSi) and Al(3OSi) units [34,35]. The time evolution of 27Al
for quantitative analysis. MAS NMR spectra shows that octahedral Al sites are intact to the
geopolymerisation reaction and only pentahedral Al takes part in
the alkaline dissolution of MK because the signal at 28 ppm almost
Table 3 disappeared within 3 h after mixing.
Mineral phase composition of red brick, metakaolin, and MK0 mixture at the age of
The 27Al NMR spectrum of the WRB powder shows only two
180 min (wt%).
separate signals. The narrow peak at 13 ppm belongs to octahedral
Component Red brick Metakaolin MK0 (180 min) Al sites. Due to its very narrow character it belongs to a highly
Anorthite 13.38 – 6.13 ordered structure, most probably to a mica type mineral which
Gehlenite 2.62 – 1.12 was also determined by XRD analysis. The main wide band located
Hematite 2.75 – 1.12
between 40 and 80 ppm is an overlap of several superposed signals
Orthoclase 8.88 – 3
Quartz 29.37 11.86 20.25 associated with tetrahedral Al in anorthite, gehlenite, mica and
Mica 19.75 1.12 4.25 orthoclase crystalline phases and amorphous aluminosilicate
Calcite 1.50 – 0.25 phase. Within the first 60 min after mixing, the octahedral Al signal
Anatase – 0.62 and the shoulder at 67.9 ppm completely disappeared; hence, it is
Corundum – 1.75
Amorphous phase 21.75 84.65 63.88
presumed that these two signals belong to the same species. The
slight change in the chemical shift of the main broad peak from
61.1 to 58.3 ppm indicates an increase in the level of condensation
of the aluminosilicate network. The NMR spectra of the MK25,
resented by the main band centred at 1043 cm1. When the alka-
MK50, and MK75 mixtures were only a superposition of the MK0
line activator is added, a slight shift towards a lower wavenumber
and MK100 spectra and thus are not presented here in detail.
can be recognized (curves b–d). This shift is associated with the
depolymerisation of MK structure due to alkaline hydrolysis and
the subsequent formation of new predominantly cyclic oligomer 5. Discussion
species [27]. This assumption is supported by the presence of a
weak band at 867 cm1, which is attributed to symmetric stretch- In the study, a constant water-to-solid ratio was used in order
ing in isolated orthosilicate molecules. In the spectra which are to prevent the mixing water from influencing the rheological and
associated with the geopolymerisation of WRB powder an opposite mechanical properties of the prepared geopolymers, although dur-
effect can be observed. Since WRB powder is a heterogeneous ing practical applications the same workability should be main-
material composed of many different mineral phases, the main tained and thus the amount of mixing water would differ. The
band is extremely broad compared to that found in the MK spec- rheological behaviour of the geopolymer mixture based on MK as
trum. After 60 min the main band became slightly narrower but an aluminosilicate precursor substantially differs from that which
no shift was observed. The shift towards a higher wavenumber first is based on WRB powder. A strong thixotropic effect indicates
appeared after 180 min. The shift in the position of the main band the existence of attraction forces between MK particles in the fresh
over time is clearly presented in Fig. 10. Two very weak bands at paste which are able to resist Brownian motion. This is caused by
796 and 776 cm1 can be assigned to OAAlAO bending vibrations dipole–dipole interactions between the edges of aluminosilicate
and SiAOASi symmetric stretching vibrations [28,29]. The FTIR layers in the metakaolin and the molecules of sodium silicate acti-
spectrum of the non-activated MK50 mixture is very similar to that vator, which result in the flocculation of the metakaolin particles.
recorded for pure metakaolin. However, after 120 and 180 min the The evidence for this behaviour was also supported by time-
main band shifts towards a lower wavenumber and the spectra dependent oscillation measurements. For the mixtures that exhib-
represent a simple combination of the MK0 and MK100 mixtures. ited thixotrophy, i.e. MK50, MK75 and MK100, the gel point, which
 P. Rovnaník et al. / Construction and Building Materials 188 (2018) 924–933
Fig. 9. FTIR spectra in the absorbance mode of the time evolution of geopolymerization of MK0, MK50, and MK100 mixtures: a) aluminosilicate precursor; b) 60 min;
c) 120 min; d) 180 min.
Fig. 10. Shift over time in the position of the Si–O–T asymmetric stretching band
for MK0, MK50, and MK100 geopolymer mixtures.
is defined as the point when curve G0 crosses curve G00 , was not
observed because this phenomenon had already occurred before
the measurement started.
The initial viscosity increased with decreasing WRB/MK ratio.
The relatively high viscosity of MK-based geopolymer is mainly
controlled by the viscosity of the alkaline silicate solution, which
has been already reported by Favier et al. [19,20]. In our study,
the difference in viscosity between MK-based and WRB-based
geopolymer can be partially attributed to the different granulome-
try of the aluminosilicate precursors. MK has a much narrower par-
ticle distribution than WRB, and its largest particle size is five
times lower. As a result, MK has a larger specific area and adsorbs
more mixing water, which causes a reduction in the amount of rhe-
ological fluid. Another viscosity-enhancing effect is associated with
the irregular spiny plate-like structure of metakaolin particles
(Fig. 13).
The time evolution of plastic viscosity also depends on the
WRB/MK ratio. Almost no change in viscosity was observed for
the mixtures with a high proportion of WRB powder (MK0 and
MK25). This is mainly caused by the lower reactivity of WRB pow-
931
Fig. 11. 27Al MAS NMR spectra of the time evolution of metakaolin geopolymer-
ization: a) metakaolin; b) 60 min; c) 120 min; d) 180 min.
der due to its less amorphous character compared to MK, which
was proven via quantitative XRD analysis (Table 3) and by
obtained pozzolanic activity values (Table 1). The gelation process
of pure WRB-based geopolymer started approximately 120 min
after mixing, which was indicated by a slight increase in viscosity
and was also confirmed by changes in molecular structure.
Although the gel point determined from oscillation measurements
was not achieved until after 480 min, the change in the chemical
shift of the main peak in 27Al MAS NMR spectra from 61.1 to
58.3 ppm and shift of the wavenumber from 971 to 991 cm1 in
FTIR are associated with the formation of more condensed species,
which already occurred between 120 and 180 min. However, the
932 P. Rovnaník et al. / Construction and Building Materials 188 (2018) 924–933
Fig. 12. 27Al MAS NMR spectra of the time evolution of WRB geopolymerization:
a) red brick; b) 60 min; c) 120 min; d) 180 min (*denotes spinning sidebands).
Fig. 13. SEM micrograph of the morphology of metakaolin particles.
condensation degree was still very low at this age and according to
the value of the loss factor (tan d > 1) the MK0 mixture still exhib-
ited viscous rather than elastic behaviour. The time evolution of
viscosity observed for the MK50, MK75 and MK100 mixtures was
quite different. The viscosity of the mixtures with a high propor-
tion of MK gradually decreased within the first 120 min. This is
associated with the partial dissolution of metakaolin in highly
alkaline solution and its subsequent condensation to primary
aluminosilicate oligomer units with much preferably cyclic than
linear character [27]. Due to alkaline hydrolysis, the polycondensa-
tion degree decreased and caused a shift of the main band in FTIR
to a lower wavenumber (Fig. 10). Since no isolated AlO4 units were
indicated by 27Al MAS NMR, it is presumed that they are very reac-
tive and immediately combine with silicate molecules from the
activator to form oligomers with partially condensed Al(3OSi)
and fully condensed Al(4OSi) units, which were already observed
as signals at 70 ppm and 58.3 ppm, respectively, after 60 min of
the reaction [36]. These highly concentrated oligomers are prone
to immediate gelation [37], which causes a considerable increase
in yield stress (Fig. 5). The condensation reactions are associated
with the release of additional water molecules, which improves
the rheological properties. The viscosity of the MK50, MK75 and
MK100 mixtures then remained constant due to two antagonistic
effects – the release of water, which acts as a thinning agent, dur-
ing the condensation process, and the gelation of aluminosilicate
oligomers that finally results in the formation of larger molecules.
Since MK is more reactive and shows a lower degree of crystallinity
than WRB powder, its gelation process is more rapid and con-
tributes to the faster evolution of the yield stress.
The substantial difference in rheology between MK-based and
WRB-based geopolymer mixtures is mainly caused by the different
microstructure of both aluminosilicate precursors. MK is highly
reactive due to the distorted structure of the pentacoordinated Al
layer, which is responsible for metakaolin’s amorphous character,
whereas in WRB powder crystalline mineral phases predominate
and only 20% is amorphous matter. Although it is not anticipated
that crystalline species would take part in the geopolymerisation
reaction, XRD analysis proved that the structure of WRB powder
is transformed during alkali-activation from rather ordered to
more disordered. The combination of the XRD and 27Al MAS NMR
analyses showed that part of the mica-type mineral, containing
tetra- and hexacoordinated Al, is dissolved within 60 min after
mixing and then transformed into amorphous or pseudocrystalline
geopolymer gel.
Finally, the rheological testing results for the MK-based
geopolymer are consistent with results reported by Favier et al.
[19,20], which indicate its high viscosity and very low yield stress
value. On the other hand, the viscosity of WRB-based geopolymer
is 24 times lower even with the same activator concentration
and type, and hence it cannot be exclusively controlled by the vis-
cosity of the interstitial fluid but also by the type and shape of the
solid particles, which is in contradiction with certain conclusions
presented in ref. [20]. The substitution of up to 25% of WRB with
MK has an almost negligible influence on the time-dependent rhe-
ological properties of geopolymer mixtures but the strong influ-
ence of highly reactive metakaolin becomes evident when more
than 50% of MK is used.
6. Conclusions
Five different geopolymer mixtures with metakaolin and red
brick powder as aluminosilicate precursors were tested for their
mechanical and rheological properties and the results were corre-
lated with microstructural analysis performed by X-ray diffraction,
FTIR, and MAS NMR. The mechanical properties of hardened
geopolymer depend on the reactivity of the aluminosilicate precur-
sor, and therefore higher compressive and flexural strengths were
achieved for mixtures with a higher proportion of MK except for
the pure MK-based mixture. This implies that WRB and MK clearly
have a synergistic effect on the mechanical properties of geopoly-
mer because the best values were achieved for the MK75 mixture,
which has the ratio WRB/MK = 25/75.
Measurement of flow parameters revealed that substitution of
MK-based geopolymer mixture with WRB powder considerably
affects its rheological behaviour. While MK-based geopolymer is
strongly thixotropic, the thixotropic effect disappeared when 75%
of the MK was replaced with WRB. The substitution of MK also
caused a decrease in the plastic viscosity of the fresh geopolymer
mixture, but it had no effect on the yield stress value, which was
close to zero for all mixtures.
The time evolution of the plastic viscosity and yield stress
markedly depends on the type of aluminosilicate precursor used
in the geopolymer mixture. Since metakaolin contains mainly
amorphous phase with a distorted aluminum layer structure, it is
 P. Rovnaník et al. / Construction and Building Materials 188 (2018) 924–933
more reactive than WRB powder and undergoes rapid dissolution
followed by the immediate gelation of aluminosilicate oligomers,
resulting in a gradual increase in yield stress. The more WRB pow-
der is used in the initial mixture, the more delayed is the evolution
of yield stress that can be observed. The relatively rapid dissolution
of MK in alkaline activator solution and the subsequent increase of
the amount of free water due to the condensation of isolated AlO4
and SiO4 units leads to a drop in viscosity, and thus an improve-
ment in the workability of mixtures with more than 50% of MK.
On the other hand, the replacement of WRB powder with up to
25% of MK has an almost negligible effect on the rheological prop-
erties of blended WRB/MK-based geopolymer. Generally, it was
proved that the rather problematic workability of MK-based
geopolymer mixtures can be improved either by prolonged mixing
or by the partial substitution of MK with WRB powder.
Although WRB powder is less reactive than MK, which is mainly
due to its lower content of reactive amorphous phase, the
microstructural analysis showed that the proportion of amorphous
matter increased by 42% within 180 min during the geopolymer-
ization of WRB. This finding reveals that part of the crystalline
phase in WRB is subjected to alkaline dissolution and takes part
during the process of geopolymerization.
Conflict of interest
None.
Acknowledgements
This outcome has been achieved with the financial support of
the Czech Science Foundation, project No. 16-02862S, and the
MEYS CR under ‘‘National Sustainability Programme I”, project
No. LO1408 (AdMaS UP). CIISB research infrastructure project
LM2015043 funded by the MEYS CR is gratefully acknowledged
for its financial support for the measurements performed at the
CF Cryo-electron Microscopy and Tomography.
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