Advances in Cement Research Advances in Cement Research

http://dx.doi.org/10.1680/jadcr.17.00092
Paper 1700092
Influence of low-pozzolanic activity Received 16/05/2017; revised 31/08/2017; accepted 04/09/2017
calcined mica clay on hydration and Keywords: calcined clays/Portland cement/pozzolans

hardening of Portland cement ICE Publishing: All rights reserved

Kaminskas, Monstvilaite and Valanciene

Influence of low-pozzolanic activity calcined

mica clay on hydration and hardening of
Portland cement
Rimvydas Kaminskas Virginija Valanciene
Professor, Department of Silicate Technology, Chemical Technology Faculty, Associate Professor, Department of Silicate Technology, Chemical
Kaunas University of Technology, Kaunas, Lithuania (corresponding author: Technology Faculty, Kaunas University of Technology, Kaunas, Lithuania
rimvydas.kaminskas@ktu.lt)
Deimante Monstvilaite
PhD Student, Department of Silicate Technology, Chemical Technology
Faculty, Kaunas University of Technology, Kaunas, Lithuania

This study investigated the possibility of using artificial materials obtained during combustion of mica clay as an
additive for Portland cement. The mica clay granules were burned at 7001100C for 1 h. It was considered that the
pozzolanic activity of the investigated mica clay would depend on the combustion temperature. The highest
pozzolanic activity (134 mg calcium oxide (CaO)/g) was observed in the samples calcined at a temperature of 900C. In
the samples, 5, 10, 15 and 25% (by weight) of the Portland cement was replaced with calcined additive at the
temperature of 900C. The samples were then hardened for 28 d under normal conditions. Owing to relatively low
pozzolanic activity, the pozzolanic reaction in the samples with the additive up to 28 d of hydration was not
noticeable. However, calcined mica clay additive acted as a microfiller and significantly increased the rate of hydration
of Portland cement clinker minerals. The calcined mica clay additive had a positive effect on the compressive strength
of samples cured for 28 d under normal conditions because up to 15 wt% of ordinary Portland cement can be
replaced with the additive being investigated without impairing the strength class of the cement.

Introduction replaced to improve long-term strength and durability

A pozzolanic material is defined as a siliceous or siliceous and
aluminous material, without direct cementitious value;
however, in the presence of moisture, it reacts chemically with
calcium hydroxide (at ordinary temperatures) to form com-
pounds possessing cementitious properties (ASTM C618
(ASTM, 2015); Said-Mansour et al., 2011). Recently, pozzo-
lans have been of particular interest because their application
reduces overall environmental impact and cost when mixed
with Portland cement (CEM I) in blended cement systems.
The use of pozzolans reduces the carbon dioxide emitted
per tonne of product and can also improve various physical
properties of the resulting concrete (Donatello et al., 2010).
For this reason, environmental concerns can be dealt with by
replacing a part of the Portland cement clinker with pozzolanic
materials in mortars and concretes (Sabir et al., 2001; Samet
et al., 2007; Tironi et al., 2012).
Pozzolans can be naturally occurring minerals or industrial
by-products (Donatello et al., 2010). The major benefit of
blended cements is improved durability, due to the reaction
between the pozzolana and excess calcium hydroxide
(Ca(OH)2) produced by cement hydration to form calcium
silicate hydrate (CSH) gel, which reduces the porosity of the
binder (Donatello et al., 2010).
Calcined clay is one of the earliest known pozzolanic materials
and, depending on the pozzolanic activity of the calcined clay,
this material allows part of the cement in concrete to be
(Chakchouk et al., 2009; Saikia et al., 2002). The calcining
temperature producing the active state is usually in the range
of 600800C, which causes the destruction of the crystalline
structure of the clay and formation of amorphous silica and
alumina (Elinwa, 2006).
The properties of calcined kaolinitic clay have been actively
investigated. Kaolinitic calcined clay, which is an abundant
material, has gained importance as an alternative pozzolanic
material (Habert et al., 2008, 2009; Tironi et al., 2012). It is
known that, during the dehydration process, kaolinite loses
1376% of its weight because Al2O32SiO22H2O is trans-
formed into Al2O32SiO2 (Morsya et al., 2008). The transform-
ation temperature of this process depends on the crystallinity
and particle size of kaolinite. At the temperature of 700C,
kaolinite decomposes completely and transforms into the
amorphous phase (metakaolinite) (Shvarzman et al., 2002).
The main feature of metakaolin is its high pozzolanic activity.
Metakaolinite reacts with calcium hydroxide to form calcium
silicate and calcium aluminate hydrates (Kjellsen and
Lagerbland, 1995).
The origin of clay, for example mica clay, has hardly been
investigated. Usually, mica clay deposits contain a mixture of
different clay minerals (kaolinite, illite, montmorillonite,
palygorskite and others) and a large proportion of impurities
of non-clay materials, such as quartz, calcite, feldspars, mica,
anatase and sulfides (Tironi et al., 2012). Heat treatment of

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 Advances in Cement Research Influence of low-pozzolanic activity
calcined mica clay on hydration and
hardening of Portland cement
Kaminskas, Monstvilaite and Valanciene

clay materials in a kiln (a process known as calcination) is the
most common method to influence the pozzolanic reactivity of
the mineral by functionally removing the hydroxyl groups that
maintain the layered structure and creating metastable, poorly
crystalline, anhydrous aluminium silicates (Taylor-Lange et al.,
2015). He et al. (1995) reported that, after heat treatment,
kaolin and some montmorillonites had the highest pozzolanic
activity, but the rest of the clay materials could be
considered of low pozzolanic activity. Also calcite or other clay
impurities reduce the pozzolanic activity during the com-
bustion of clay. This behaviour was explained by the dilution
effect of the most active clay minerals (Zunino and Scrivener,
2017).
The aim of this work was to determine the possibility of using
an artificial material obtained during the combustion of mica
clay as an additive for Portland cement.
Materials and methods
The chemical composition and characteristics of the mica clay
taken from an industrial quarry are shown in Table 1. The clay
was chopped, dried at 40 2C for 24 h, and ground using a
ball mill to a specific surface area of 30 m2/kg. The granules
(12 2 mm) of the clay investigated were formed from dried
clay and the powder was later wetted. The water-to-solid ratios
of the mixtures were 04. The granules obtained were dried
again at 40C for 24 h and then burned at different tempera-
tures (samples were kept at the given temperature for 1 h;
heating rate of 10C/min). After burning, the samples obtained
were crushed by a Fritsch jaw crusher Pulverisette 1 and
ground with a Fritsch planetary disc mill Pulverisette 9 for
40 s at 600 r/min.
The ordinary Portland cement (OPC) CEM I 425 R was used
in this research. The chemical composition of the cement is
shown in Table 1. The mineralogical composition of the OPC
is as follows: 3CaOSiO2, 5297 wt%; 2CaOSiO2, 1961 wt%;
3CaOAl2O3, 916 wt%; 4CaOAl2O3Fe2O3, 974 wt%;
CaSO42H2O, 537 wt%.
The samples for the compressive strength analysis (prisms
4  4  16 cm) were formed according to European standard
BS EN 196-1 (BSI, 2016a) (the cement-to-sand ratio was 1:3,
and the water-to-cement (w/c) ratio was 05). The samples were
kept in moulds at 20 1C and 100% humidity during the first
day of hydration. After 24 h of hydration, the samples were
transferred to deionised water and were stored there for 27 d at
20 1C. To make an accurate estimation of the hydration
process, the samples for the instrumental analysis were pre-
pared without the sand. The storage conditions of the samples
were analogous to those used during the strength test. The
hydration of samples was stopped using acetone: three
samples were kept under the conditions described; then
samples were crushed separately, milled together using a
laboratory planetary disc mill, passed through an 80 sieve,
washed with acetone, and then dried in a carbon dioxide
(CO2)-free atmosphere at 80 5C for 8 h. A representative
amount was selected from the lot to be analysed, which upon
further quartering (BS EN 196-2 (BSI, 2013)) was reduced to
a manageable amount for appropriate sample preparation.
Powder samples were stored in sealed bags to prevent carbona-
tion and hydration.
The tests of the setting time and normal consistency were
performed according standard BS EN 196-3 (BSI, 2016b).
The pozzolanic activity was assessed using the modified
Chapelle method (Raverdy et al., 1980). This test consists of
placing 1000 g of mineral admixture into 500 ml of lime
solution (1200 g/l calcium oxide (CaO)). The solution was
kept for the first 48 h in a thermostat at the temperature of
45C. At the end of this period, 50 ml of the solution was
taken and the calcium oxide content was determined by
titration with 005 N hydrochloric acid (HCl) solution using
methyl orange as an indicator. The results were expressed
as milligrammes of bound calcium oxide per gramme of
pozzolanic additive. The rest of the solution (450 ml) was kept
again for 24 h at the temperature of 45C. The process was
repeated until the estimated value of the pozzolanic activity
was insignificantly low (7 d).

The X-ray diffraction (XRD) analysis was performed on the

Table 1. Chemical composition and characteristics of D8 Advance diffractometer (Bruker AXS, Karlsruhe,
raw materials Germany) operating at the tube voltage of 40 kV and tube
Components Clay: wt% OPC: wt%
current of 40 mA. The X-ray beam was filtered with a nickel
(Ni) 002 mm filter to select the CuK wavelength. The dif-
Silicon dioxide (SiO2) 4640 1952 fraction patterns were recorded in a BraggBrentano geometry
Aluminium oxide (Al2O3) 1420 503
using a fast counting detector Bruker LynxEye based on
Iron (III) oxide (Fe2O3) 940 305
Calcium oxide (CaO) 103 6139 silicon strip technology. The specimens were scanned over the
Magnesium oxide (MgO) 415 393 range 2 = 370 at a scanning speed of 6/min using a
Potassium oxide (K2O) 303 106 coupled two theta/theta scan type.
Sodium oxide (Na2O) 016 012
Sulfur trioxide (SO3) 006 25
The chemical composition analysis of the samples was per-
Loss on ignition 1146
Specific surface area: m2/kg 290 350 formed by X-ray fluorescence spectroscopy (XRF) on a Bruker
X-ray S8 Tiger WD spectrometer equipped with a rhodium

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 Advances in Cement Research Influence of low-pozzolanic activity
calcined mica clay on hydration and
hardening of Portland cement
Kaminskas, Monstvilaite and Valanciene

(Rh) tube with an energy of up to 60 keV. The measurements 160 Q C calcite

of powder samples were carried out in a helium atmosphere 140 D dolomite
Q quartz
and the data were analysed with Spectra Plus Quant Express H haematite
120
software. I ilite

Intensity: a.u.
100 K kaolinite
M montmorillonite
Simultaneous thermal analysis (STA) (differential scanning 80
calorimetry (DSC) and thermogravimetry (TG)) was carried 60 C
out on a Netzsch STA 409 PC Luxx instrument with ceramic 40 Q
M D K Q
sample handlers and crucibles of platinumrhodium (PtRh). 20 I K C D
K K M HKQ C
D I CC H C Q
At a heating rate of 15C/min, the temperature ranged from
0
30C to 1000C under the ambient atmosphere. 3 8 13 18 23 28 33 38 43 48 53 58 63
2: degress
The particle size distribution and the specific surface area of
the materials used were determined by a laser particle size Figure 1. X-ray diffraction analysis of dried clay
analyser (Cilas 1090 LD) in intervals from 01 to 500 m. The
distribution of solid particles in the air stream was 1215 wt%.
Compressed air (2500 mbar) was used as a dispersing phase. 2 0
The measuring time was 15 s.
1
0

Mass change: %
4
Heat flow: mW

The calorimetric analysis data were obtained using a Tam Air 2

III calorimeter. The range of measurement was 600 mW, the
4 8
sensitivity of the signal was 4 W, the time constant was
<500 s, the temperature of the experiment was 25 01C and 6
the water-to-solid ratio was 05.
2 12
8

Results and discussion
Calcined clay
According to the XRD analysis data (Figure 1), kaolinite
(d-spacing: 0715, 0447, 0357, 0249, 0233 nm; JCPDS
75-0938), montmorillonite (d-spacing: 1400, 0309 nm;
JCPDS 03-0016), illite (d-spacing: 1000, 0502, 0200 nm;
JCPDS 26-911), haematite (d-spacing: 0270, 0251,
0169 nm; JCPDS 72-0469), quartz (d-spacing: 0425, 0334,
0245, 0181, 0154 nm; JCPDS 46-1045), dolomite (d-spacing:
0288, 0219, 0178 nm; JCPDS 83-1766) and calcite
(d-spacing: 0302, 0228, 0209, 0189, 0186 nm; JCPDS
72-1650) were found in dried clay at the temperature of 40C.
In the DSC curve of clay (Figure 2, curve 1), the first
endothermic effect up to 180C is ascribed to the removal of
moisture from the clay and the second endothermic effect at
550C is ascribed to dehydroxylation of kaolinite (Palomo
et al., 1999). A significant endothermic peak observed at
780C was mainly due to decomposition of carbonates. The
exothermic effect at 300450C is ascribed to burn-out of
organic materials. It was determined (Figure 2, curve 2) that
the total weight loss of the sample was 1146 wt%.
In the next stage of investigation, the clay was calcined at the
temperatures of 700, 800, 900, 1000 and 1100C for 1 h. In the
XRD curve of the clay burned at the temperature of 700C
(Figure 3, curve 1), the clay mineral kaolinite decomposes
because the main peaks of this compound disappear in the
XRD curve. When the burning temperature was increased to
10 16
30 130 230 330 430 530 630 730 830
Temperature: C
Figure 2. Simultaneous thermal analysis curves (curve 1, DSC;
curve 2, TG) of mica clay
800C, the beginning decomposition of the carbonates and the
structural damage of illite and montmorillonite are observed
in the XRD curve (Figure 3, curve 2). Moreover, compared
to the dried sample, additional formation of haematite
(d-spacing: 0270, 0251, 0169 nm; JCPDS 72-0469) and
melilite (d-spacing: 0318, 0256, 0191 nm; JCPDS 72-1412) is
observed in the sample burned at 800C. In the XRD curve of
the sample calcined at 900C (Figure 3, curve 3), the further
damage of illite, full decomposition of montmorillonite and
formation of melilite, haematite and diopside (d-spacing:
0295, 0289, 0252, 0197 nm; JCPDS 17-0318) were noticed.
No remaining peaks, characteristic to calcite, illite and mon-
tmorillonite are observed in the sample burned at the tempera-
ture of 1000C (Figure 3, curve 4). Quartz, melilite, diopside
and haematite were found in clay calcined at the temperature
of 1100C (Figure 3, curve 5).
It was determined that the pozzolanic activity of investigated
mica clay depends on the combustion temperature
(Figure 4(a)). When the burning temperature increased from
700 to 900C, the pozzolanic activity of calcined mica clay
(CMC) grew from 104 mg CaO/g to 134 mg CaO/g. This

3
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 Advances in Cement Research Influence of low-pozzolanic activity
calcined mica clay on hydration and
hardening of Portland cement
Kaminskas, Monstvilaite and Valanciene

C calcite D dolomite
Q
~ Q quartz H haematite
I ilite A diopside
L melilite
M montmorillonite
L A 5 CMC1100
Q A
L A A
A H A Q Q
Q
A
Q
A H Q Q

Q 4 CMC1000
L A
A AA H AQ Q Q
L A Q A H Q Q
A
Intensity: a.u.

Q
A
3 CMC900
I I L A A
L AA H AQ Q Q
Q Q Q
A A H
~

C
Q

I 2 CMC800
I L Q Q
M Q
A CA M H HA D QC A CC H H
Q Q
~
C

Q
I 1 CMC700
M I Q
L D AQ C Q
C D Q A C C Q Q
A M H H H H

3 6 9 12 15 18 21 24 27 30 33 36 39 42 45 48 51 54 57 60 63 66 69
2 : degrees

Figure 3. X-ray diffraction pattern of CMC at different temperatures: curve 1, calcined at 700C; curve 2, calcined at 800C; curve 3,
calcined at 900C; curve 4, calcined at 1000C; curve 5, calcined at 1100C

growth of pozzolanic activity is associated with decomposition After milling calcined clay granules, the obtained additive can
of montmorillonite because kaolinite has already decomposed also be used as a microfiller (BS EN 12620:2002 + A1:2008
at a lower temperature. Structural damage of illite does not (BSI, 2002)) as 100 wt% of the particles are lower than
have a positive impact on pozzolanic activity because further 100 m and the uniformly distributed particles are dominated
increase in the combustion temperature had a negative effect by diameters of less than 30 m, constituting 70 wt% of the
on the pozzolanic activity of burned mica clay. The decrease of total amount (Figure 5).
pozzolanic activity is caused by the formation of the inert
phase and integration of active silicon dioxide (SiO2) and
aluminium oxide (Al2O3) into the composition of other Influence of CMC additive on the hydration of
compounds (diopside, melilite). Thus, the highest pozzolanic Portland cement
activity of the additive investigated (134 mg CaO/g) is signifi- In the next stage of the research, the influence of CMC at the
cantly lower than other widely used pozzolanic additives, the temperature of 900C on the hydration and hardening of
activity of which reaches 350600 mg CaO/g (Rodier et al., Portland cement was investigated.
2017; Sabir et al., 2001).
The data of the setting time and normal consistency
Despite the fact that CMC was distinguished by relatively low (Table 2) show a negligible decrease in the setting time
pozzolanic activity at the temperature of 900C, the Frattini and a continuous increase in the normal consistency, corres-
test (BS EN 196-5 (BSI, 2011)) (Figure 4(b)), performed ponding to the growing percentage of added CMC.
additionally, shows that the samples with 15 and 25 wt% of These effects are related to the partial substitution of
this additive satisfy the test for pozzolanicity because the data cement with calcined clay, causing excessive consump-
points of these samples are plotted below the curve of calcium tion of water and absorption of part of the water for
ion saturation concentration. hydration.

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 Advances in Cement Research Influence of low-pozzolanic activity
calcined mica clay on hydration and
hardening of Portland cement
Kaminskas, Monstvilaite and Valanciene

To assess the influence of the CMC additive on the initial performed (Figure 6). The rate of heat evolution was calcu-
hydration of cement, the measurement of heat evolution lated on the basis of a unit weight of OPC. Thus, the rates can
during the hydration process (calorimetric analysis) was be compared with each other, and the contribution of the
CMC additive can be separated out.

140
Two intense peaks of heat evolution were found on the calori-
120 metric curves of the investigated samples. The first, an active
heat evolution, is caused by wetting a cement powder and an
100
initial kinetic reaction, during which Ca2+, OH, SiO4 4, and
mg CaO/g

80 SO4 2 ions passed into the solution, and the second is related
to the reaction between the deeper layers of calcium silicate
60 particles and water (Snelson et al., 2008).
40
The results show that the CMC additive insignificantly shor-
20 tened the duration of the induction period. Compared with the
0 analysis results of pure cement samples (1 h 33 min), the
700 800 900 1000 1100 induction period was reduced to 1 h 22 min or 1 h 30 min
Temperature: C when 10 or 25 wt% of cement was replaced by CMC, respect-
(a) ively. During the hydration of cement samples with the CMC
additive, at the second exothermic reaction period, a slightly
18
100 OPC + 5 CMC later heat flow than in the pure cement sample was identified
16 95 OPC + 10 CMC on the released heat flow measurement curve (Figure 6(a)).
14 85 OPC + 15 CMC The maximum heat flow value was reached after 8 h 7 min of
75 OPC + 25 CMC hydration in the sample with 5 wt% additive and 8 h 6 min in
12
[CaO]: mmol/l

the sample with 25 wt% additive, whereas in the pure cement

10
sample it was reached after 8 h.
8
6 In addition, the second peak of all samples with CMC additive
4
produces an increase in the maximum heat evolution rate
relative to OPC, and this effect grows as the amount of
2
additive increases.
0
35 55 75 95 In the second peak of heat evolution, at the later hydration
[OH]: mmol/l period, a shoulder is observed that is associated with an
(b)
aluminate hydration reaction and with the final formation of
Figure 4. Results of pozzolanicity tests: (a) Chapelle method; ettringite (Hesse et al., 2011). The CMC additive had an influ-
(b) Frattini test ence on the aluminate hydration reaction. In the samples with
the CMC additive, this shoulder was fixed earlier than in OPC

100
1 50
80
Cumulative values: %

Histogram: 10, %

40
60
30

40
20

20 10
2

0 0
004 14 46 14 36 90 240
Diameter: m

Figure 5. Distribution of milled CMC additive particle size: 1, cumulative values; 2, histogram

5
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 Advances in Cement Research Influence of low-pozzolanic activity
calcined mica clay on hydration and
hardening of Portland cement
Kaminskas, Monstvilaite and Valanciene

Table 2. Influence of CMC additive on normal consistency and It should be noted that more heat of hydration was identified
setting time of OPC in samples with the CMC additive during the hydration
Amount of Normal Initial Final process. The heat of hydration proportionally increased with
additive: consistency setting time: setting time: the increased amount of the CMC additive in the cement
wt% (w/c): % min min samples (Figure 6(b)). The induced heat was slightly higher for
0 0276 89 139 samples with 5 and 10 wt% CMC (280 J/g) than for pure
5 0283 85 135 cement (278 J/g), and even reached 292 J/g for samples with
10 0287 82 135 25 wt% CMC after 48 h of hydration.
15 0289 80 130
25 0293 72 122
Therefore, it can be assumed that the CMC additive acceler-
ates the early stage of the hydration of OPC and its individual
compounds.
0.0045

0.0040

0.0035 Compressive strength

Investigation of the compressive strength of the samples, in
Heat flow: W/g

0.0030
which the content of CMC pozzolana additive varied from
0.0025
5 to 25 wt%, showed that the effect on the strength properties
0.0020 100 OPC + 0 CMC of cement samples depends on the amount of the additive
0.0015 95 OPC + 5 CMC
used. It was estimated (Figure 7) that, after 7 d of hydration,
90 OPC + 10 CMC
0.0010 samples with 5 wt% CMC pozzolana additive had higher
85 OPC + 15 CMC
0.0005 75 OPC + 25 CMC
compressive strength and samples with 10 wt% CMC additive
0 had approximately the same compressive strength as that of
05 20 35 50 65 80 95 110 125 140 155 170 185 200 215 the OPC samples. The lowest compressive strength was for
Age: h samples with 25 wt% of additive. When the hydration time was
(a) increased up to 28 d, the compressive strength of the samples
300
with 5 and 10 wt% CMC pozzolana additive (522 and
516 MPa, respectively) remained higher than that of the OPC
250 samples (509 MPa). Even the samples with 15 wt% CMC
additive (468 MPa) belong to the same strength class (425) as
Hydration heat: J/g

200 the OPC samples. Thus, the CMC pozzolana additive had a
positive effect on the strength properties of Portland cement
150
100 OPC + 0 CMC and up to 15 wt% of ordinary cement can be replaced with the
95 OPC + 5 CMC
100 additive investigated without impairing the strength class
90 OPC + 10 CMC
of cement.
85 OPC + 15 CMC
50
75 OPC + 25 CMC

0
05 55 105 155 205 255 305 355 405 100 OPC + 0 CMC 85 OPC + 15 CMC
Age: h 600 95 OPC + 5 CMC 75 OPC + 25 CMC
(b) 90 OPC + 10 CMC
Compressive strength: MPa

500
Figure 6. Calorimetric curves of (a) thermal flow and (b) heat in
samples with different amounts of the CMC additive
400

300
samples and its intensity was higher (except for the sample
with 5 wt% CMC) than the heat flow maximum of the 200
calcium silicate hydration reaction. Thus, the CMC additive
100
accelerated the reaction of aluminate-bearing phases.
Presumably, this heat evolution phenomenon is related to
0
active aluminium compounds that had been formed during 7 28
the burning of the additive investigated: a greater release of Time: d
aluminate ions causes a faster consumption of gypsum,
Figure 7. Compressive strength of cement samples with different
leading to an earlier intense exothermic peak for the aluminate amounts of CMC additive after 7 and 28 d of hydration
reaction.

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 Advances in Cement Research Influence of low-pozzolanic activity
calcined mica clay on hydration and
hardening of Portland cement
Kaminskas, Monstvilaite and Valanciene

C calcite E etringire
CS calcium silicate P portlandite
Q quartz B brownmillerite
CSH calcium silicate hydrate
P Q
P 5 75 OPC + 25 CMC
CS
C CSH CSH P
P P C
E E CS P B CSH P CS
C B P C P CS CS P

P
P
CS 4 85 OPC + 15 CMC
Q
C CSH CSH P
P P C P
E CS P CS
E C B P C B CSH CS P CS P
Intensity: a.u.

P
P
3 90 OPC + 10 CMC
C CS
Q CSH CSH P
E P P C P
E CS P CS CS
C B P C B CSH P CS P

P
P

CS P 2 95 OPC + 5 CMC
C CSH CSH
C
E P Q P CS P P CS
C B P C CS
E B CSH P CS P

P
1 100 OPC + 0 CMC
P
CS

C CSH P
CSH
E P P C
CS P P CS CS
C B P C B CSH P CS
P

3 8 13 18 23 28 33 38 43 48 53 58 63 68
2 : degrees

Figure 8. X-ray diffraction patterns of cement samples with CMC additive cured for 28 d under normal conditions

XRD analysis
The results of XRD analysis (Figure 8) showed that, after 28 d
of hydration, in all X-ray patterns of the samples, the diffrac-
tion peaks of unhydrated calcium silicates (d-spacing: 0304,
0277, 0260, 0218 nm; JCPDS 42-551) and brownmillerite
(d-spacing: 0725 nm; JCPDS 30-226) were identified. The dif-
fraction peaks of quartz (d-spacing: 0425, 0334 nm; JCPDS
77-1060) were identified only in the samples with CMC
additives (Figure 8, curves 25) because silicon dioxide is an
integral part of calcined clay and, with an increasing amount
of additives, the intensity of the quartz peaks increases.
In addition to this, in all XRD curves, the characteristic peaks
of calcite (d-spacing: 0303, 0228 nm; JCPDS 5-586) were
observed. The formation of calcium carbonate (CaCO3) is
related to the carbonation process of the samples. Peaks
characteristic of calcium silicate hydrate (d-spacing: 0304,
0279, 0182 nm; JCPDS 33-306) and portlandite (d-spacing:
0492, 0311, 0262, 0192 nm; JCPDS 44-1481, 84-1271) were
identified in the XRD curves of all samples. The intensity of
unhydrated calcium silicates peaks decreases with an increasing
amount of CMC additive from 5 to 25 wt% in the samples.
The lower intensity of unhydrated calcium silicates peaks may
be associated with a more intense hydration process of this
compound. To conclude, based on XRD analysis results, it can
be stated that the CMC additive does not substantially modify
the hydration process of Portland cement samples.
Thermal analysis
In all of the DSC curves (Figure 9) of 7 and 28 d hydrated
samples, endothermic effects at 80200C, 440460C and
700760C were observed. The first endothermic peak belongs
to the dehydration of many cement hydration products
(such as calcium silicate hydrates, calcium aluminium hydrates
and ettringite), whereas the endothermic effect at 435465C
indicates the decomposition of portlandite. The endothermic
effect at 700760C belongs to the decomposition of carbon-
ates, which are the result of carbonation of cement samples.
As all of the DSC curves were almost identical, the results of
DSC analysis after 7 d of hydration were excluded from
Figure 9. The results of TG analysis are listed in Table 3.
The results of TG analysis (Table 3) showed that when the
amount of additive was increased up to 25 wt%, after 7 d of
hydration, the mass loss due to the presence of portlandite
(435465C) proportionally decreased. Furthermore, the
higher mass loss was determined on the OPC sample at the
area (80200C) of decomposition of many cement hydration
products (mainly calcium silicate hydrate). After 28 d of
hydration, the trend of mass loss during decomposition of

7
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 Advances in Cement Research Influence of low-pozzolanic activity
calcined mica clay on hydration and
hardening of Portland cement
Kaminskas, Monstvilaite and Valanciene

silicate hydrates can be formed during pozzolanic reaction

75 OPC + 25 CMC between active amorphous compounds of additive used and
85 OPC + 15 CMC calcium hydroxide. In this case, there should be decreased
quantity of portlandite formed; however, in the samples with
90 OPC + 10 CMC the CMC additive a larger amount of portlandite was found
Heat flow: a.u.

95 OPC + 5 CMC than in the pure Portland cement samples. Thus, pozzolanic
reaction in samples with the CMC additive up to 28 d of
100 OPC + 0 CMC hydration is not noticeable, but this additive acts as a micro-
filler, constitutes nucleation sites of calcium hydroxide crystals
and accelerates the hydration of clinker particles (Menndez
et al., 2003) because both calcium silicate hydrates and
calcium hydroxide were formed in the samples with the addi-
tive. This influence of the CMC additive explained a high
compressive strength of the samples with this additive after
30 130 230 330 430 530 630 730 830 28 d of hydration (Figure 7).
Temperature: C

Figure 9. Differential scanning calorimetry patterns of samples

with CMC additive cured for 28 d under normal conditions Conclusions

& The pozzolanic activity of the investigated mica clay

depends on the combustion temperature. The highest
Table 3. Thermogravimetric analysis results of samples cured for pozzolanic activity (134 mg CaO/g) was observed in the
7 and 28 d under normal conditions samples calcined at the temperature of 900C.
& In the samples with 15 and 25 wt% calcined at the
Mass loss: wt%
temperature of 900C, this additive satisfies the Frattini
Amount of After 7 d After 28 d test for pozzolanicity; however, owing to relatively low
CMC of hydration of hydration pozzolanic activity, the pozzolanic reaction in the
additive: samples with the CMC additive up to 28 d of hydration
wt% 90200C 435465C 90200C 435465C
is not noticeable.
0 475 251 486 265 & Calcined mica clay additive acted as a microfiller,
5 470 241 593 336 significantly increased the rate of the hydration of Portland
10 444 240 595 308
cement clinker minerals and had a positive effect on the
15 402 202 542 268
25 392 182 480 196 compressive strength of samples cured for 28 d under
normal conditions. Up to 15 wt% of ordinary cement can
be replaced with the additive investigated without
impairing the strength class of cement.
major cement hydrate drastically changed. The mass loss at
80200C in all samples with the CMC additive (except the
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