Composites: Part B 57 (2014) 155–165

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Composites: Part B
journal homepage: www.elsevier.com/locate/compositesb

High strength metahalloysite based geopolymer

Vladimir Zivica ⇑, Martin T. Palou, Tomáš Ifka Ľ. Bágeľ
Institute of Construction and Architecture, Slovak Academy of Sciences, Slovakia

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

Article history: The unique properties of aluminosilicates had made them valuable in the wide range of industrial appli-
Received 19 March 2012 cations. One branch of application represents building materials. A significant factor of the level of the
Received in revised form 19 August 2013 quality of engineering properties of building materials anyhow is the water/binder ratio. It is well known
Accepted 15 September 2013
that its decreasing value effectively increases strength and quality of other engineering properties of the
Available online 26 September 2013
material. Due to the accompanying effect impairing workability of the mixture for processing the pres-
sure compaction is needed.
Keywords:
The subject of the paper are the results of the study of the properties of metahalloysite based geopoly-
B. Microstructures
B. Strength
mer prepared under the use of the combination of very low water/metahalloysite ratio (0.08), pressure
D. Mechanical testing compaction of the fresh mixture by applying an uniaxial compressive stress of 300 MPa and alkali acti-
E. Compressive molding vation. The effect of preparation conditions was systematically studied by thermal analysis (DTA, GTA),
mercury intrusion porosimetry, scanning microscopy and compressive strength estimation of the geo-
polymer. The used metahalloysite was a product of calcination of the source material at 650 °C 4 h. It
was an amorphous material showing an increased thermodynamic unstability and herewith an increased
reactivity in comparison with the unheated solid.
The metahalloysite based geopolymer pressure compacted paste reached after 24 h of the hardening
compressive strength of 76.2 MPa whereas the reference paste only 0.03 MPa. It represents 2540 times
increase in behalf of the pressure compacted paste. High compressive strength was evidently the conse-
quence of the found high homogeneous and dense pore structure of the pressure compacted paste.
The regression analysis shown for the geopolymer binder systems a polynomial empirical equations as
an appropriate configuration. For the alkali activated slag and Portland cement systems the exponential
configuration was suitable. The cause of the difference may be apparent phase composition. It was pro-
nouncedly amorphous structure of the geopolymer binder systems opposite to the combined amorphous
and crystalline structures distinctive for alkali-activated slag and Portland cement binder systems. Then
the resulted different destruction mechanism under the loading, at the strength test of the material.
For the elucidation of the causality more detailed research is needed.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction dependence of the engineering properties of concretes and other

Geopolymers are a class of aluminosilicates formed by reaction
of alkali solution with dehydroxylated clay or analogous solid
waste materials under high alkaline conditions. The hardening
mechanism involves the chemical reaction of geopolymeric pre-
cursors, such as alumino-silicate oxides, with alkali polysilicates
yielding polymeric Si–O–Al bonds. The result of the hardening
mechanism is a three dimensional zeolitic framework unlike tradi-
tional hydraulic binders [1–7].
This circumstance is a cause of significant differences in the
quality and variety of the engineering properties of the composites
based on geopolymer and current cements. Geopolymers can gain
strength more rapidly then Ordinary Portland cement. The
⇑ Corresponding author.
E-mail address: usarziv@savba.sk (V. Zivica).
cement composites on the value of water/cement ratio (w/c) is
very well known. Also the fact that their strengths, durability
and the quality of other engineering properties are increased when
the w/c values are decreased [1–3]. A significant factor limiting the
use of this positive effects is the decrease of the workability of the
fresh composite mixture and the decrease of the quality of the
engineering properties of the hardened composite. A limited solu-
tion enables the use of the plasticizers or the superplasticizers. An
illustration of the influence and significance of the w/c ratio used
shows Fig. 1.
A very attractive solution represents the combination of super
low w/c ratios, under w/c 0.1 resulting in a submicroscopic pore
structure and an adequate high quality of the engineering proper-
ties of the composite [4–10]. It appears that the low porosity ce-
ment composites have a great potential of reconsideration and
modification of composition and structure [11]. All mentioned

1359-8368/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.compositesb.2013.09.034
156 V. Zivica et al. / Composites: Part B 57 (2014) 155–165
Fig. 1. Dependence of compressive strength of the cement paste on total porosity
and changes of w/c ratio.
dependences and effects are common also to geopolymer systems
distinguishing from the related cement materials only by the spe-
cific properties of geopolymer as a binder. The significance of the
water: cement ratio for the geopolymer systems is reported by
Barbosa et al. [12]. According to the authors the effects of the
changes of water:cement ratio on the properties of the geopoly-
mers are the same like at cement materials. Similar is the effect
of ambient temperature increase showing the setting time de-
crease as a consequence of increase of rapidity of polymerization
and the hardening more rapidly than OPC cement. But only the
temperature increase to 90 °C seems to be optimal [13–17]. The
aim of the presented work was to study on the possibilities of
the use of effects of the combination of very low w/c ratio and
pressure compaction in the geopolymer cement systems. As a
model the alkali activated metahalloysite system was used. Metah-
alloysite used was a product of its heating. Halloysite is an end
member of kaolin group of clay minerals and it is composed of kao-
lin like kaolinite. The properties of the heated halloysite may vary
due to the influence of mineral composition which is complicated
by presence of minor elements and impurities in the clay lattice
and by nonclay minerals [18,19].
Progressive heating of clays leads to the removal of free, ad-
sorbed and structural water, which is followed by the formation
of new minerals. In open atmospheric conditions include reversible
dehydration of loosely bound water when dry-heated between
100 °C and 300 °C, irreversible removal of interlayer water and loss
of swell potential at temperature above 400 °C, dehydroxylation or
release of hydroxide groups from the crystal structure between
500 °C and 1000 °C, silicate recrystallization and the formation of
new minerals above 800 °C [20–22].
Some physico-chemical properties of clays such as swelling,
plasticity, cohesion, compressibility, strength, cation exchange
capacity, particle size, adsorptive properties, pore structure, sur-
face acidity, and catalytic activity as well mineralogy are greatly af-
fected by thermal treatment. The investigation of these effects and
their influence on the properties of the clays has a great impor-
tance [23–25].
The thermal transformation of clays is dependent on the heat-
ing parameters such as temperature, heating rate and time, as well
as, cooling parameters significantly influence the dehydroxilation
process. The major quantitative criterion for evaluating the perfor-
mance by thermal analysis is a degree of dehydroxilation. In dehy-
droxilation region the activity of heated material increases along
with the temperature but decreases abruptly in the ‘‘spinel’’ region.
The activities can be measured by the compressive strength of pre-
pared geopolymer.
The behavior of geopolymers at high temperatures exposure is
significantly dependent on the chemical composition of the binder
itself, especially on the type of alkali ion, and on the type of high-
temperature phases built up [26]. The type of charge-compensat-
ing cation, Si/Al ratio and crystal structure themselves are the sig-
nificant factors also [27,28].
The metakaolin geopolymer suffered strength loss exposed to
temperatures up to 800 °C. It is interesting that fly ash geopolymer
gained strength after the same high temperature exposure. Results
show a strength drop of 34% in metakaolin geopolymer while fly
ash-synthesized counterparts had strength increase of 6% after ele-
vated temperature exposures. According to the authors the cause is
the different pore structure character of the materials. The metaka-
olin geopolymer pores are predominantly composed of mesopores
whereas fly ash geopolymer pores contain higher proportion of
micropores than metakaolin geopolymer [29].
While numerous studies on the calcination of kaolinite have
been conducted much less attention has been paid to the thermal
transformation of halloysite, nevertheless the heating has
undoubtedly a significant influence on the properties of halloysite
[30,31]. The situation is evidently a consequence of the fact that
the reaction mechanism under heating of halloysite has been pos-
tulated to be analogous to that of kaolinite because halloysite is
structurally and chemically similar to kaolinite. But halloysite pos-
sesses a tabular morphology in contrast to the plate-like nature of
kaolinite. The textural and morphological characteristics of heated
halloysite, accordingly, should be different from those of kaolinite
[18,30,31]. It is evident that heating causes extensive changes in a
broad spectrum of the properties also of halloysite, offering poten-
tial uses from the production of versatile ceramic and novel clay
mineral nanocomposites including construction materials
[12,32,33].
The significant fact is that the burning of clays produces mate-
rial, that harden when mixed with lime and water. It is due to the
fact that clay gains a pozzolanic activity when burned at tempera-
ture between 600 °C and 900 °C. This artificial pozzolana is mostly
composed of silica and alumina [34].
Thermally treated or calcined clays display a higher reactivity
during geopolymerization than non-calcined material. Calcification
activates material by changing their crystalline structure into
amorphous structure to store extra energy and increase its activity
and increasing compressive strength [35]. The calcining tempera-
ture of the clay affects the pozzolanic reactive state. Calcination
also affects the amount of Al and Si released from source material.
Higher the temperature used during calcination process, shorter
the time is needed to obtain the material that gives the maximum
compressive strength [36,37].
2. Experimental
2.1. Test specimens preparation and their testing
For the study the metahalloysite pastes prepared with activator
solution/metahalloysite ratio (l/s) 0.08 and compacted in the fresh
state by applying of the uniaxial pressure of 300 MPa were used.
The test specimens were 20 mm-edge cubes. The reference test
specimens were prepared with l/s 0.70 compacted by hand. The al-
kali activator sodium hydroxide solution was added to the mixture.
The portion of the activator corresponded to 7 wt.% of the weight of
the metahalloysite. Depending on the l/s ratio used, molar ratio
H2O/Na2O was 22.3 at the reference paste and 0.023 at the com-
pacted paste. In addition for the purpose of the regression analysis
and the mutual comparison were prepared the test specimens
from metakaolin based geopolymer, alkali-activated blast furnace
slag, and Portland cement. The experimental conditions were the
 V. Zivica et al. / Composites: Part B 57 (2014) 155–165
same as described. But compacted by the pressures 100, 200 and
300 MPa. The metahalloysite test specimens were completed by
compaction pressures 100 and 200 MPa.
The preparation of the fresh mixtures represented an intensive
mixing for 3 min using electrical mixer. The forms were filled by
the mixture and then exposed to the uniaxial pressure of
300 MPa with the endurance of 1 min. The preparation of the ref-
erence test specimens was the same but manual compaction was
used. The prepared test specimens hardened 24 h in the forms, at
temperature 20 °C and relative humidity 95%. After the demolding,
their testing followed. The test specimens were dried at 105 °C and
these properties were estimated: bulk weight and compressive
strength, specific weight, phase composition, pore structure and
morphology of the matrix.
2.2. Methods used
Bulk weight was calculated using the estimated weight and
dimensions of the test specimens. For the estimation of compres-
sive strength was used a destructive method using the loading
press. Thermal analysis was carried out on the equipment Thermal
analysis METTLER TOLEDO, TGA/DSC 1, STAREe System, the sample
mass 45 mg, heating rate was 10 °C/min, ramping from ambient
temperature to 1000 °C in an air atmosphere. Pore structure was
analyzed using the intrusion mercury porosimeter mod. 2000 Erba
Science working to the pressure 200 MPa with macro-pore unit
120, under the use of the contact angle 141.3° and surface tension
480 dyn/cm of mercury. Using the pore analyze results the water
permeability coefficients were calculated [38]. The morphology
of the samples was studied by scan electron microscopy using a
Carl Zeiss – EVO 40 HV microscope. Before the scanning process,
all samples were coated with gold to enhance the electron conduc-
tivity. For specific weight estimation the equipment Pentapyc
5200e QUANTACHROME CORPORATION was used. Solution heat
was estimated by the method of kinetics of heat development
[39,40].
3. Results and discussion
3.1. Properties of the materials used
3.1.1. Chemical composition
The data on the materials used are given in Tables 1 and 2. As it
can be seen in Table 1 the consequences of the heating of halloysite
was the increase in the content of SiO2 and Al2O3, and increase in
the specific weight. It was evidently a consequence of minimizing
the ignition loss content due to the heating. The increase of SiO2
and Al2O3 content seems to be interesting effect because their ratio
used to be appreciated as a factor significant for the development
of mechanical properties of geopolymers. This ratio is considered
as a main synthesis parameter among alkali content Na2O/Al2O3,
Table 1
Chemical composition of halloysite and metahalloysite used.
Material Halloysite
Chemical composition (%)
Humidity 2.66
Ignition loss 10.08
SiO2 54.93
Al2O3 28.07
Fe2O3 2.01
CaO 1.75
MgO 0.56
Specific weight (kg m3) 2476
Solution heat (J g1) 370.4
157
water to aluminosilicate ratio, and processing parameters such as
curing time and curing temperature and others [41–44]. At the gi-
ven case the used metahalloysite accounted the SiO2/Al2O3 molar
ratio 3.27.
The significance of SiO2/Al2O3 molar ratio is based on the fact
that a high silicate dosage is necessary for synthesizing alumino-
silicate gel that provides good interparticle bonding and physical
strength of geopolymers. The silica content controls the dissolution
and polymerization of silica and alumina in alumino-silicate gel.
High reactive silica content involved the formation of high amount
of alkali–alumino-silicate gel and consequently a high mechanical
strength was developed in the resulting material [45]. Geopoly-
mers with SiO2/Al2O3 molar ratio in the range of 3.16–3.46 had
better strength which decreased with increasing ratio up to 3.86
[46,47]. But, the compressive strength almost lineary increases
with silica content up to 4.0. Further increase in silica content of
mix reduced compressive strength. It was found that at higher con-
tent of silica beyond the threshold value of 4.0 leads to a reduction
in reactivity showed by the decrease of compressive strength. It
was found that at higher silica content, the polymerization of alu-
minosilicate gel is not favoured. Instead, the dissolved precursors
tend to form zeolites which are weaker on compressive strength
[41]. The information shows that SiO2/Al2O3 molar ratio represents
a significant factor in the synthesis of geopolymers significantly
influencing the resulted compressive strength and undoubtedly
further engineering properties of the geopolymers. The different
optimal ratio values signify the dependence on the synergizm of
the further technological factors. Like for example along the SiO2/
Al2O3 molar ratio increase, the predominant amorphous structure
and the fine particle size of fly ashes, are appropriate for the syn-
thesis of geopolymers with a SiO2/Al2O3 molar ratio of 1 or 2.
[47,48]. The major quantitative criterion for evaluation of the per-
formance of clay by thermal treatment is degree of the dehydrox-
ilation Dtg [49]. Dtg = 1  (M/Mmax), where M and Mmax are residual
and maximum sample mass loss, respectively. The dehydroxilation
of pure halloysite in ambient atmosphere results in mass loss at
about 14% and. Dtg = 1, which corresponds to mass in bound hydro-
xyl ions in halloysite. Using data on the ignition loss (Table 1) the
found value of dehydroxilation degree for the used metahalloysite
was Dtg = 0.87. This value shows the deficient dehydroxylation of
the used metahalloysite. Evidently, the higher calcination temper-
ature or longer holding time should be used for the total dehydr-
oxylation and accomplishing the Dtg = 1.
The significance of the SiO2/Al2O3 molar ratio in the process of
geopolymer formation can be appreciated as a significant but not
unique determining actuator cooperating with the other incoming
technological elements. The SiO2/Al2O3 molar ratio of the used
metahalloysite 3.27 occurs in the mentioned optimal region for
the development of consequent compressive strength.
3.1.2. Solution heat
The results of solution heat development method indicate the
information on the state of destroying of crystalline structure of
halloysite due to its heating and thermodynamical instability and
reactivity of the heated product – metahalloysite. The loss of com-
Metahalloysite bined water due to the thermal treating causes the crystalline net-
work of the clay mineral to be destroyed, while silica and alumina
0.38 remains in a messy, unstable amorphous state. Thermally treated
1.33 or calcined clays display a higher reactivity during geopolymeriza-
62.12
32.25
tion that non-calcined material. Calcination activates material by
1.98 changing their crystalline structure into amorphous structure to
1.60 store extra energy and increase its activity [50]. As it can be seen
0.42 in Table 1 the used metahalloysite showed 12 times increased
2530
solution heat. The increased solution heat indicates thermodynam-
4469
ical unstability and increased reactivity of the metahalloysite in
158 V. Zivica et al. / Composites: Part B 57 (2014) 155–165

Table 2
Chemical composition and properties of metakaolin, blast furnace slag and Portland cement used.

Material Metakaolin Blast furnace slag Portland cement CEM 52.5

Humidity 0.35 – –
Ignition loss 1.95 2.81 0.97
SiO2 53.68 35.77 20.68
Al2O3 42.00 9.55 6.74
Fe2O3 1.70 0.27 2.15
CaO 0.21 38.83 64.72
MgO 0.10 12.83 1.37
Specific weight (kg m3) 2582 2954 3240
Specific surface area (m2 kg1) – 470 359

the process of geopolymer synthesis opposite to the unheated
halloysite.
3.1.3. Thermal analysis
The thermal analysis for the study of the heating effects and
dehydration and dehyroxilation processes of clays is a very quali-
fied method.
The DTA curve of halloysite, showed in Fig. 2, characterizes: The
effect with peak temperature 80 °C, corresponding to the first mass
loss due to the dehydration of interparticle water, adsorbed water,
and interlayer water. Then, endothermic effect with temperature
peak 524 °C, beginning at ca 400 °C and ending at ca 570 °C corre-
sponding to the dominant mass loss due to the dehydroxilation, re-
lated to the release of OH groups from the octahedral layer. The
shape, and area of dehydroxilation peak can be affected by particle
size distribution, crystallinity, type of isomorphous substitution,
mechanical treatment and impurities [51,52]. An exothermic peak
at 985 °C on the DTA curve corresponding to the recrystallization
can be also observed.
The DTA curve of the product of calcination (Fig. 3) shows only a
broad endothermic peak covering the area beginning at ca. 300 °C
and ending at ca. 960 °C. Its occurrence is evidently the conse-
quence of the presence of the amorphous aluminosilicate product
of the calcination. Again the exothermic peak at 984 °C is observa-
ble again connected with the recrystallization of the calcination
product [53–55].
3.1.4. Pore structure
A knowledge of the change of pore structure parameters of the
clays due to their heating is a useful element in the microstructural
characterization of such materials. These changes need to be taken
into account in interpreting experimental results [56–58]. Some
presentation of the characterization of shape and size of pores in
halloysite offered nitrogen adsorption and desorption isotherms.
Calculations from these isotherms indicate that halloysites with
mainly small particles (<0.08 lm wide) had abundant cylindrical
pores with narrow size distribution in the 5–15 nm range. They
also indicate that halloysites with mainly large particles (>0.1 lm
wide) had few if any pores in the mesopores range (2–50 nm) [59].
Gas sorption was used because comparisons of gas sorption
measurements with those made using mercury intrusion porosi-
metry indicate that only gas sorption, which measures smaller
pore sizes than mercury porosimetry, would enable determination
of the sizes of the dominant fine pores in at least some of the hal-
loysites [60]. An increase in specific surface area between 12 °C and
900 °C calcination temperature is reported. This effect may have

Fig. 2. Thermoanalytical data on halloysite.

 V. Zivica et al. / Composites: Part B 57 (2014) 155–165
Fig. 3. Thermoanalytical data on metahalloysite.
been due to the formation of micropores during surface breakage
resulting structural rearrangement or transformation of the parti-
cles [53].
The found pore structure parameters of halloysite and its
heated product are presented in Table 3. Showing these differ-
ences: 62% and 740.4% increase of pore volume and specific surface
area and macropore portion and pore median decrease represent-
ing 19.1 and 17.3% of metahalloysite opposite to the halloysite.
The pore volume and specific surface area increase can be assigned
to the dehydration and dehydroxilation effects and surface break-
age effect as it is reported in the paper [53]. All these effects make
the pore structure of metahalloysite more accessible for the alkali
activator solution contributing to the development of geopolymer
synthesis. The found pore median and macropore content decrease
indicate also the refining of pore structure again as factors aiding to
the reactivity of the halloysite.
4. Metahalloysite based geopolymer pastes
4.1. Mechanical properties and pore structure parameters
The results of the estimation of bulk weight, compressive
strength and pore structure parameters are summarized in Table 4.
The significant increase in compressive strength and bulk weight of
Table 3
Pore structure of halloysite and metahalloysite used.
Pore structure parameter Halloysite
Pore volume (mm g )3 1
555
Macropore portion (%) r > 7500 nm 21.5
Pore median (nm) 1118
Total porosity (%) 74.9
Specific surface area calculated from 4.7
porosimetry data (m 2g1)
In brackets – changes opposite to the original values.
159
the pressure compacted paste opposite to the reference is evident.
Also the decrease in total porosity and water permeability. For
comparison the metahalloysite based geopolymer pressure com-
pacted paste reached compressive strength of 76.2 MPa whereas
the reference paste only 0.03 MPa. It corresponds to the ratio in-
crease of 2540 in behalf of the pressure compacted paste.
These effects are in a good relation with the changes of pore
structure characteristics. Figs. 4–7 show histograms and cumula-
tive pore size curves of the pastes. The pressure compacted paste
showed a significant shift of cumulative pore size curve and the
maxima of histogram in the area of nano-pores with radius under
100 nm. It shows the compacted paste as a material with the in-
creased pore structure homogeneity and much finer advanced pore
structure opposite to the reference paste. It may have an interest-
ing and significant consequence for the strength characteristics of
the material.
Compressive strength is an interesting and important engineer-
ing property of the cement composites, including geopolymers.
The related data reported in the literature present a broad spec-
trum of compressive strength values of the geopolymer based
materials, ramping from several MPa to tens. It is due to the fact,
that their compressive strength depends on a number of factors
including gel phase strength, the ratio of the gel phase/undissolved
Al–Si particles, the distribution and the hardness of the undis-
solved Al–Si particle sizes and their amorphous nature [12,33–38].
For the attained strength are hydration products significant,
while pores have a negative effect on strength. For alkali – acti-
vated systems the following main factors determining their
Metahalloysite strength are significant: the nature and finesess of the starting
903 (+62.7%) material, curing regime and time of the hardening, especially
17.4 (19.1%) water/aluminosilicate material ratio.
925 (17.3%) Beside already mentioned significance of SiO2/Al2O3 and Na2O/
81.4 (+2.5%)
Al2O3 molar ratios, also the pH of the initial alkali metal silicate
39.5 (+740.4%)
precursor control significantly compressive strength development
of the forming geopolymer, The high alkali content was found to
promote solid solution but also caused alumino-silicate gel
160 V. Zivica et al. / Composites: Part B 57 (2014) 155–165

Table 4
Properties characteristics of the metahalloysite pastes after 24 h of the hardening.

Properties characteristics (%) Pressure compacted paste Reference paste Difference (%)
Activator solution to slag ratio 0.08 0.70 9.1
Bulk weight (kg m3) 1575 970 +162.4
Compressive strength (MPa) 76.2 0.03 +254000
Density (kg m3) 2008 1981 +101.4
Total porosity (%) 24.3 51.0 47.6
Total pore volume (mm3 g1) 79 446 17.7
Porosity (%) 15.7 49.9 31.5
Pore median (nm) 59 423 13.9
Portion of pores r over 100 nm (%) 17 71 24.9
Portion of pores r under 100 nm (%) 83 29 +86.2
Specific surface area (m2 g1) 5.5 16.3 33.7

50
180
45
Portion of pores (% vol.)

160
40

Pore volume (mm3/g)

140
35
30 120

25 23 100
21
20 80
14 13
15 12 60
9
10 40
4
5 1 1 1 20
0 0 0 0 0 0 0
0 0
1 10 100 1000 10000
3

10

00

0
10

00
10

10

Pore radius (nm)

Pore radius (nm)
Fig. 6. Cumulative pore size curve of the pressure compacted metahalloysite based
Fig. 4. Histogram of the pressure compacted metahalloysite based geopolymer
geopolymer paste after 24 h of the hardening.
paste after 24 h of the hardening.

50 500
Hls
Hls 450
Portion of pores (% vol.)

45
Pore volume (mm3/g)

40 400
35 350
30 300
25 22 250
20 17 200
15 12 150
8 9
10 8
6 5 5 100
4
5 1 2 1 50
0 0 0 0
0 0
1 10 100 1000 10000
00
10

00
3

10

0
10

10

Pore radius (nm)

Pore radius (nm)
Fig. 7. Cumulative pore size curve of the reference metahalloysite based geopoly-
Fig. 5. Histogram of the reference metahalloysite based geopolymer paste after mer paste after 24 h of the hardening.
24 h of the hardening.

precipitation at very early stages resulting in lower compressive significant. Elimbi et al. reported the compressive strength of
strength [38]. The effect of curing temperature and time is also sig- metakaolin based geopolymer between ca 10 and 35 MPa, when
nificant. A mere increase in synthesis temperature is sufficient to kaolin calcined at 500–700 °C was used [39]. According to Yang
increase the level of long-range ordering in geopolymeric binders et al. fly-ash based geopolymers after 28 days of the hardening
[39]. An adequate curing is required to achieve advanced mechan- achieved the compressive strength between 5 and 10 MPa. When
ical and durability performance. The setting time is of practical the ground granulated blast furnace slag was added it was possible
importance since it defines the time required for transport, placing to reach the increase of compressive strength values between ca 22
and compaction of the fresh geopolymer mixture [41]. and 52 MPa [42]. Metakaolin geopolymer with ratios SiO2/Al2O3
As an example for compressive strength geopolymers can be the 3.3–4.5, Na2O/SiO2 0.25–0.45 and H2O/Na2O 10–25 at the curing
following data. The compressive strength of F-type fly ash geopoly- at room temperature for 60 min, then at 65 °C for 90 min and dried
mer shown compressive strength between 5 and 60 MPa, at the at 65 °C for 60 min. After 24 h of the hardening reached the com-
duration of the hardening between 1 and 28 days. Also it has been pressive strength between 1 and 48 MPa [43].
found that the effect of heat treatment temperature and its dura- It is evident that the geopolymers show compressive strength
tion on the density of F-type fly ash based geobricks was not predominantly the values of several MPa, from 5 to 50 MPa. This
 V. Zivica et al. / Composites: Part B 57 (2014) 155–165 161

range by the found value of 75 MPa, as result of the presented

work, was overcome significantly. Undoubtedly, it was a conse-
quence of the essential change in processing conditions based on
the use of the combination of very low of activator solution to
metahalloysite ratio and pressure compaction. However, it is inter-
esting that pressure compacted metakaolin based geopolymer
shown significantly higher compressive strength 146.6 MPa [61].
The cause is not completely clear. But undoubtedly, the
difference in surface area, solution heat and porosity of
SiO2–Al2O3–Fe2O3 of the calcination product are presumable
factors of the unequal compressive strength of the compared
materials (Table 5).

4.2. SEM images

Fig. 8. SEM image of the pressure compacted metahalloysite based geopolymer
As it is reported unheated halloysite possesses typical hollow paste after 24 h of the hardening.
and end opened tubulate particles. Heating to 900 °C causes no evi-
dent morphological changes, only a mottling was observed at the
heating beginning at 600 °C. The mottled appearance is probably
caused by the structural disordering associated with dehydroxila-
tion and the phase separation of amorphous SiO2 and Al2O3
[62,63].
In Figs. 8 and 9 can be seen SEM images of the metahalloysite
based geopolymer pastes. No tubulate particles in both cases could
be observed in the pastes, indicating the absence of the particles of
metahalloysite in the hardened materials. It seems, that all parti-
cles for the formation of geopolymer were consumed. But the dif-
ference between morphology of the pressure compacted and
reference pastes, shown by SEM images, is evident. Whereas the
pressure compacted paste (Fig. 8) shown more dense and coherent
solid, afterward the reference paste presented incompact solid
with the occurrence of the large grains and pores as dark places
(Fig. 9). It signifies the decreased portion of geopolymer formatted
in the reference paste and slower formation of geopolymer under Fig. 9. SEM image of the reference metahalloysite based geopolymer paste after
the higher l/s ratio (0.7). Also, probably only a small quantity of 24 h of the hardening.
the geopolymer product is taking the place at the surface layer of
the metahalloysite particulates [64–67].
The SEM results shown the same tendency as it could be seen at 4.4. Mathematical correlations
the porosimetry results. This observation is linked to a strong cor-
relation in the compressive strength increase reported in the pa- In construction industry, strength is a primary criterion in
pers [15,16,19,20–22]. selecting concrete for a particular application. A rapid and reliable
prediction for the strength of concrete would be of great impor-
tance. Undoubtedly, the same significance is for geopolymer mate-
4.3. Thermal analysis results rials interesting and needed [68]. Significant and crucial is the
understanding the relationships between concrete composition,
The results of the thermal analysis of studied materials are microstructure and mechanical properties. Therefore, their mathe-
shown in Figs. 10 and 11. As it can be seen these results provided matical correlating has proved to a challenge [69]. Also the develop-
only limited information on the phase composition of system. It is ment of their properties with time and long-term stability are of a
evidently the consequence of the amorphous or near-amorphous special significance for the use of geopolymer materials in practice.
character of the constituents of the materials studied, thus a use The solution needs empirical and theoretical models accounting the
of any method is rather restricted. DTA-curves are characterized relationship between the strength as a main mechanic performance
by the occurrence of the very shallow endothermic effects between index of cement based materials and pore structure [69,70].
ca 50 and 250 °C. These, as it can be seen in DTG curves, were con- As examples can be mentioned empirical models of Hasselman
ducted with the peaks 80° and 175 °C at the pressure compacted et al. [71–75].
paste and at 80°, 145° and 240 °C at the reference one. At both In the context of these claims and efforts programming ap-
causes the presence of an exotherm with the peaks at 962° and proach for the prediction of compressive strength becomes an
972 °C can be seen. Evidently, as a consequence of mullite interesting and expanding domain [76–78]. Regression analysis
formation. was used for the assessment of empirical equations of the

Table 5
Comparison of metahalloysite and metakaolin properties.

Material SiO2/Al2O3 ratio Solution heat (J g1) Pore volume (mm3 g1) Pore median (nm) Macropore portion (%) Specific surface area (m2 g1)
Metahalloysite 3.27 4469 903 17.4 92.5 39.5
Metakaolin 2.22 5563 1016 15.5 77.2 38.7
162 V. Zivica et al. / Composites: Part B 57 (2014) 155–165

Fig. 10. Thermal analysis results of the pressure compacted metahalloysite based geopolymer paste after 24 h the hardeing.

Fig. 11. Thermal analysis results of the reference metahalloysite based geopolymer paste after 24 h the hardening.

correlation between compaction pressure-compressive strength
and compressive strength – porosity of the systems based on the
metahalloysite and metakaolin based geopolymers and for the
comparison with alkali activated blast furnace slag and Portland
cement.
The influence of compaction pressure on the development of
compressive strength of the pastes is shown in Figs. 12 and 13.
The figures demonstrate that increase of compaction pressure is
beneficial to increase the compressive strength of the materials.
Corresponding empirical equations in Table 6 are given.
 V. Zivica et al. / Composites: Part B 57 (2014) 155–165 163

It is evident that for the geopolymer binders the polynomial 160

Compressive strength MPa

configuration of the empirical equations conforms. At the alkali-
140
activated slag and Portland cement it is the exponential
120 Portland cement
configuration.
The dependence of compressive strength on the porosity of the 100
Alkali activated blast
studied materials is shown in Figs. 14 and 15. The decrease of com- furnace slag
80
pressive strength with porosity increase is evident. Corresponding
empirical equations in Table 7 are given. 60
Again for the geopolymer systems the polynomial configuration 40
of the empirical equations conform and exponential for the alkali-
20
activated slag and Portland cement systems. A different continu-
ance of the curves very good corresponds to the difference in the 0
0 50 100 150 200 250 300 350
fitness of the configuration of the empirical equations. It is evident
at the comparison of Figs. 14 and 15. Compaction pressure MPa
As it is very well known, the nature of binder is apparently one
Fig. 13. Dependence of compressive strength of Portland cement and alkali-
of the factors determining the mechanical properties of very low activated slag pastes on the compaction pressure used – after 24 h of the hardening.
porosity cement systems [79]. The observable differences between
correlations of geopolymer binder systems aside and slag and Port-
land cement binders across may be assigned to the difference in Table 6
the nature of the created hydration products and resulted porosity Empirical equations for correlations of compaction pressure-compressive strength in
the dependence on the binders.
character. According to the accessible information in the literature
the phase composition of studied binder systems can be character- Matakaolin-based geopolymer CS = 0.0008 CP2 + 0.7213 CP + 0.6607
ized as it follows [80–82]. The hydration products of the geopoly- Metahalloysite-based geopolymer CS = 0.001 CP2 + 0.5483 CP + 1.5292
Alkali-activated slag CS = 52.353 exp (0.0037 PC)
mers are mainly an amorphous three-dimensional frameworks of
Portland cement CS = 72.672 exp (0.0025PC)
SiO4 and AlO4 tetrahedral randomly interlinked by shared O atoms.
Geopolymeric binders have thus similar chemical composition as CS compressive strength (MPa), CP compaction pressure (MPa).
natural zeolitic materials but without the extensive crystalline
zeolitic structure.
The alkali-activated slag contains as a main hydration product
160
calcium silicate hydrate with low Ca/Si ratio and varying degrees
Compressive strength, Sc MPa

Metakaolin - based geopolymer

in crystallinity similar to that occurring in Portland cement paste 140
but with lower ratio Ca/Si around 0.7, a crystalline phase of a
120
Mg–Al rich phase similar to hydrotalcite, crystalline phase of
AFm type is also formed in slag activated with NaOH. Portland ce- 100
ment paste contains very poorly crystalline calciumsilicate hydrate
80
known as C–SH, with generally accepted Ca/Si molar ratio in the
range 1.5–2, ettringite, Portlandite and crystalline phase of AFm 60
type. 40
A significant difference in the phase composition in the com-
Metahalloysite - based geopolymer
pared materials is very apparent. It is characterized by pro- 20
nouncedly amorphous hydration products in the geopolymers 0
opposite to the structures totalled by the combination of crystal- 0 10 20 30 40 50 60
line or poor crystalline and amorphous components how is it in Porosity, P %
the case of Portland cement and alkali activated slag binder sys-
tems. That phase composition difference may be the hypothetic Fig. 14. Porosity – compressive strength correlations for metahalloysite and
cause of the divergency in the fitness of the configuration of the metakaolin based geopolymers pastes after 24 h of the hardening.
empirical equations. The same regularity was shown for Portland
cement and alkali activated slag binder systems when alike for

160 200
Compressive strength, Sc MPa
Compressive strength MPa

180 Portland cement

140
160
120
Metakaolin - based 140
100 geopolymer
120
80
100
60 80
Metahalloyzite-based
geopolymer 60
40
Alkali - activated blast furnace
20 40
20
0
0 50 100 150 200 250 300 350 0
0 10 20 30 40 50
Compaction pressure MPa
Porosity, P %
Fig. 12. Dependence of compressive strength of metakaolin and metahalloysite
based geopolymers pastes on the compaction pressure used – after 24 h of the Fig. 15. Porosity – compressive strength correlations for alkali-activated slag and
hardening. Portland cement pastes after 24 h of the hardening.
164 V. Zivica et al. / Composites: Part B 57 (2014) 155–165
Table 7
Empirical equations for correlations of compressive strength – porosity in the
dependence on the binders.
Metakaolin-based geopolymer CS = 0.0812 P2 + 1.8374 P + 138.84
Metahalloysite-based geopolymer CS = 0.0428 P2 + 0.5138 P + 80.994
Alkali-activated slag CS = 312.42 exp (0.0524 P)
Portland cement CS = 670.26 exp (0.0612 P)
CS compressive strength (MPa), P porosity (%).
the relationship between porosity (P) and compressive strength (C)
conformed the exponential equation as it is reported in the paper
[5]:
P ¼ 37:4 expð0:08CÞ:
5. Conclusion
The influence of activator solution/solid (s/l) ratio 0.08 and ap-
plied uniaxial compressive strength 300 MPa on the alkali acti-
vated metahalloysite binding fresh system was studied. The
results of thermal analysis (DTA, GTA), mercury intrusion porosi-
metry, scan microscopy, compressive strength estimation provided
an expressive compressive strength increase after 24 h of the hard-
ening of pressure compacted metahalloysite based geopolymer,
representing the value ca 2500 times increase – opposite to the ref-
erence material.
The results of intrusion mercury porosimetry and scanning
microscopy shown the high dense and high uniform, near-nano
pore structure formated during the hardening of the pressure com-
pacted alkali-activated metahalloysite binding system. Undoubt-
edly, the found high compressive strength was the consequence
of the character of this structure. As a one consequence of the heat-
ing was found the high heat solution of metahalloysite opposite to
the unheated solid, indicating the high thermodynamic unstability
and increased reactivity of the metahalloysite. Without a doubt
this properties may be regard as a significant partner in the geopo-
lymerization process. It is surprising that to the thermodynamic
properties of geopolymer sources practically no attention is paid
in spite of the significance of the thermodynamic characteristics
of the materials even for geopolymer technology.
Interesting results shown the estimation of the empirical equa-
tions by means of regression analysis. For the metakaolin and
metahalloysite based polymers the polynomial empirical equa-
tions have been found as an appropriate configuration. On the con-
trary, for the alkali activated slag and Portland cement pastes the
exponential configuration was appropriate. The pronouncedly
amorphous structure of the geopolymers opposite to the combined
amorphous and crystalline structure of akali-activated slag and
Portland cement seem to be one of the factors causing that differ-
ence. Probably, the different destruction mechanism under the
loading of the material, at the strength test, dependently on the
structure character is implemented.
Acknowledgements
This article has been produced with the financial assistance of
the European Regional Development Fund (ERDF) under the Oper-
ational Programme Research and Development/Measure 4.2 Trans-
fer of knowledge and technology from research and development
into practice in the Bratislava region /Project Centre for applied re-
search of composite materials for deep geothermy.
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