HBRC Journal (2018) 14, 150–158

Housing and Building National Research Center

HBRC Journal

http://ees.elsevier.com/hbrcj

Hydration and characteristics of metakaolin

pozzolanic cement pastes
Hamdy El-Diadamony a, Ahmed A. Amer a,*
, Tarek M. Sokkary b,
Samir El-Hoseny a

a
Faculty of Science, Zagazig University, Zagazig, Egypt
b
Housing and Building National Research Center, Cairo, Egypt

Received 20 April 2015; revised 6 May 2015; accepted 25 May 2015

KEYWORDS Abstract The industrial area produces lots of solid waste materials with CO2 emission. One of the
Supplementary cementing most effective ways to solve these problems is the utilization of these waste materials. The produc-
materials; tion process of cements from its raw materials produces a lot of CO2. The most effective way to
Cement hydration; decrease CO2 emission of cement industry is the substitution of a proportion of cement with sup-
OPC; plementary cementing materials. Cement blended with metakaolin (MK) is also required as a coun-
Metakaolin termeasure to reduce the amount of CO2 generation. Metakaolin (MK), Al2Si2O7, is a highly
amorphous dehydration product of kaolinite, Al2(OH)4Si2O5. The aim of our research was to inves-
tigate the effect of up to 20 wt% substitutions of OPC by MK on the hydration characteristics of
MK-blended cement pastes. The physico-chemical properties of the hardened cement pastes were
studied up to 90 days of hydration. The hydration products of some selected samples were investi-
gated using XRD, DTA and DTG techniques. The results indicated that substitution of up to
20 wt% OPC by MK as pozzolanic materials resulted in an increase in the standard water of con-
sistency, acceleration of the initial setting times, high compressive strength values at earlier ages and
improvement of the mechanical and durability properties.
ª 2015 Production and hosting by Elsevier B.V. on behalf of Housing and Building National Research
Center. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/
by-nc-nd/4.0/).

Introduction

Cement industry produces the 7% of the global CO2 emission

[1]. Researchers investigate the opportunities of how to
* Corresponding author. decrease this level. The application of different supplementary
Peer review under responsibility of Housing and Building National materials can be the proper solution for this problem. With
Research Center. the development of industry, more and more by-products or
wastes have been generated, causing serious environmental pol-
lution problems. To solve this problem, a way must be found to
Production and hosting by Elsevier consume or decrease such wastes. It has been discovered that

http://dx.doi.org/10.1016/j.hbrcj.2015.05.005
1687-4048 ª 2015 Production and hosting by Elsevier B.V. on behalf of Housing and Building National Research Center.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Hydration and characteristics cement pastes 151

many industrial wastes can be recycled as a substitute for a constant W/B ratio 0.3. MK mixture with cement
(replacement) for cement or aggregate in concrete [2]. replacement of 5, 10 and 15 wt% was prepared. The results
Supplementary cementitious materials (SCMs) are now showed that 10 wt% replacement level was the optimum level
commonly used to reduce the clinker factor of cement. These of MK content.
materials can improve concrete properties such as compressive The objectives of this study were to investigate the substitu-
strength, durability and impermeability through hydraulic or tion of OPC by MK up to 20 wt% on the hydration character-
pozzolanic activity. The main component of SCMs additive istics of MK-blended cement pastes. The physico-chemical
is usually an active amorphous SiO2. The availability of com- properties of cement pastes were determined up to 90 days.
mon used industrial by-products such as fly ash, blast furnace The hydration products of some selected samples were investi-
slag, rice husk ash, silica fume, and metakaolin. Kaolinitic gated by using XRD, DTA and DTG techniques.
clays are widely available in the earth’s crust, and a heat treat-
ment between 600 and 800 C of such clays leads to the dehy- Materials and methods of investigation
droxylation of the crystalline structure of kaolinite to give
metakaolin [3–5]. The materials used in this study are ordinary Portland cement
Metakaolin (MK), Al2Si2O7, is a largely amorphous dehy- (OPC) and kaolinite clay. OPC was provided by Suez Cement
dration product of kaolinite, Al2(OH)4Si2O5, which exhibits Company, Suez plant, El-Ain El-Sokhna, and the kaolinite
strong pozzolanic activity [6–9]. MK is processed from kaolin clay was derived from Ras Abu Zneima Zone, South of Sinai,
clay by calcination at moderate temperature (650–800 C). At Egypt.
higher temperatures (>900 C), the metakaolin undergoes Metakaolin (MK) is a product from dehydroxylation of a
further reactions to form crystalline compounds, the clay mineral, kaolinite, which is very fine powder prepared
end-products being free silica and mullite. It contains silica by firing in a muffle furnace from room temperature up to
and alumina in an active form which will react with CH. The 800 C for 2 h. The ground MK passed through 90 lm B.S.
principal reasons for the use of clay-based pozzolans in mortar sieve. The chemical and physical properties of starting materi-
and concrete have been materials availability and durability als are shown in Table 1.
enhancement. In addition depending on the calcining tempera- The mineralogical composition of MK is seen from XRD
ture and clay type, it is also possible to obtain enhancement in pattern in Fig. 1. It shows the presence of quartz as the main
strength, particularly during the early stages of curing. The very mineral and amorphous alumino-silicate phase, and the amor-
early strength enhancement is due to a combination of the filler phous phase is formed as a result of reactions between SiO2
effect and accelerated cement hydration [10]. Subsequently, and Al2O3 as well as fluxing oxides impurities oxides at high
these effects are enhanced by the pozzolanic reaction between temperature. The mix composition of MK-pozzolanic cement
MK and the CH produced by the hydration of the cement. is shown in Table 2.
The reactivity of MK has been linked to its content of penta- Mixes were prepared by substitution of OPC with 5, 10, 15
coordinated aluminum ions that are formed during the dehy- and 20 wt% of MK. The dry constituents of each mix were
droxylation process [9,11]. The pozzolanic activation of MK mechanically mixed for one hour in a porcelain ball mill using
by various activators (calcium hydroxide (CH), sulfates as well four balls to attain complete homogeneity, then kept in airtight
as alkali hydroxide) and the properties of these binders have containers for further investigation. The standard water of con-
been previously reported [2]. The principal reaction between sistency as well as initial and final setting times was determined
MK and CH was derived from cement hydration, in the pres-
ence of water. This reaction forms additional cementitious
CSH gel, together with crystalline products, which include cal-
cium aluminate hydrate and alumino-silicate hydrates Table 1 Characteristics of OPC and metakaolin.
(C2ASH8, C4AH13 and C3AH6). The crystalline products
OPC MK
depend principally on the MK/CH ratio and reaction tempera-
ture [4,13]. This reaction, which is even slower than the hydra- (a) Oxide composition, %
tion of plain Portland cement improves the binding properties CaO 62.72 0.28
of blended cements [11]. SiO2 20.68 55.10
Al2O3 4.90 34.10
Production of concrete with the incorporation of industrial
Fe2O3 3.35 5.24
waste not only provides an effective way to protect the envi- MgO 2.64 0.25
ronment, but also leads to better performance annually, and SO3 2.65 0.01
it is possible to completely consume most of the industrial Na2O 0.11 0.10
waste in the world, provided that suitable techniques for indi- K2O 0.14 0.02
vidual waste incorporation are available [14]. Many research- TiO2 0.12 2.00
ers have shown a lot of interest in MK as it has been found P2O5 0.10 1.00
to possess both pozzolanic and microfiller characteristics [6]. L.O.I 2.73 1.50
The replacement with 30 wt% of MK leads to substantial (b) Blaine surface area (cm2/g) 3400 11,000
improvement in strength and transport properties of blended
(c) Residue on sieve (%):
concrete when compared to that of unblended concrete [15].
90 lm 0.00 1.00
Inclusion of MK as partial replacement of cement enhanced
45 lm 12.00 12.80
the compressive strength of concrete, but the optimum replace-
ment level of OPC by MK was about 20 wt% [14]. Dinakar (d) Specific gravity (g/cm3) 3.15 2.65
et al. [16] studied the effect of incorporating MK on the (e) Insoluble residue (%) HCl/Na2CO3 0.45 63.45
mechanical and durability properties of high strength concrete
152 H. El-Diadamony et al.

50 1
1= Quartz

40

Intensity
30

1
20

1
10 1

10 20 30 40 50
2-Theta Scale

Fig. 1 XRD pattern of MK.

31.5
Table 2 Mix composition of different OPC–MK pozzolanic w/c Is Fs 220
cement blends, wt%.

Intial and Final setting time, min

31.0 Fs
Mix. no. OPC M1 M2 M3 M4
200

Water consistency, %
OPC 100 95 90 85 80
MK 00 05 10 15 20 30.5 w/c
180

30.0
Is 160
according to ASTM methods using Vicat apparatus [17]. The
mixing of OPC and blended cement dry mixtures was carried 29.5 140
out with the required water of consistency and the fresh pastes
were first cured with their molds at 100% relative humidity for
29.0 120
24 h as described in a previous work [18]. After 24 h, the spec-
0 5 10 15 20
imens were demolded and cured under water until the desired
Metakaolin content, wt%
curing times of 3, 7, 28 and 90 days. The hydration reaction
of the pastes was stopped using an acetone–methanol mixture Fig. 2 Water of consistency, initial and final setting times of
[19]. The powdered sample was dried at 70 C for 2 h, and kept OPC and OPC–MK pozzolanic cement pastes.
in airtight containers for further investigation. The rate of
hydration was followed by the determination of free lime [20].
The combined water content was determined from the ignition the initial and final setting times of cement pastes due to coat-
loss of the dried paste at 900 C for 20 min. The bulk density, ing effect of MK particles on the cement grains as well as the
compressive strength and the total porosity were determined formation of ettringite and the dilution of OPC. As MK
as described elsewhere [21]. The hydration products of some increases (15–20 wt%) the initial and final setting times are
selected pastes were characterized using XRD, DTA and accelerated due to the slight decrease of water of consistency
DTG techniques. of cement pastes and filling effect of MK. Generally, setting
of binary MK–OPC pastes does not show consistent changes
Results and discussion with increase of MK content whereas 15–20 wt% of MK leads
to shorten the setting times. So, the increase of MK levels was
Water of consistency and setting times not proportional to replacement level [23].

The water of consistency, and initial and final setting times of
the neat OPC and OPC–MK blended cement pastes are repre-
sented in Fig. 2. Water of consistency of the net OPC cement
paste was 30%, then increased with increasing MK content up
10 wt% and decreased at 20 wt% MK. The substitution of 5
and 10 wt% of OPC by MK increases the water of consistency
of MK-pozzolanic cement pastes up to 30% and 50% respec-
tively. This is due to the high reactivity of MK, very high speci-
fic surface area and its amorphous structure. Therefore, it
needs more water of consistency [22]. The increase of MK con-
tent up to 20 wt% decreases the water of consistency from
30.50% to 29.50%. This is due to the dilution effect of OPC
by larger amounts of MK; the excessive amounts of MK act
as a filler. OPC replacement by MK up to 20 wt% elongates
Chemically combined water content
The combined water contents of OPC and OPC–MK poz-
zolanic cement pastes are graphically plotted as a function of
curing time in Fig. 3. The combined water contents increase
gradually with the increase of curing time for all cement pastes
as a result of the progressive hydration of anhydrous cement
phases as well as pozzolanic reaction and formation of
increasing amounts of hydration products. It is clear that the
chemically combined water content increases with increasing
MK content up to 10%. This is mainly due the increase of
water of consistency of cement pastes and very high specific
surface area of MK [24] which reacts with CH liberated from
hydration of OPC with the formation of additional hydration
Hydration and characteristics cement pastes
18
17
Combined water contents, %
Combined water
------ Free lime
16
15
14
13 OPC
M1
M2
12
M3
M4
11
1 10
Curing time, days
Fig. 3 Chemically combined water as well as free lime contents
versus age of hydration of OPC and OPC–MK pozzolanic cement
pastes.
products, mainly as calcium aluminosilicate hydrates (gehlen-
ite hydrate C2ASH8), calcium aluminate hydrate (C4AH13)
and calcium silicate hydrate (CSH) in the pozzolanic cement
pastes which have higher water contents than those of CSH
in the neat OPC paste [25].
As the amount of MK increases to 15–20 wt% the com-
bined water content decreases. This is mainly attributed to
the dilution of OPC which has higher rate of hydration than
MK as well as low water of consistency that decreases the rate
of hydration. 10–15 wt% MK substitution acts as a nucleating
agent which accelerates the rate of hydration of cement paste.
Free lime content
The free lime contents of OPC and OPC–MK pozzolanic
cement pastes are graphically represented as a function of
hydration age in Fig. 3. The free lime content of OPC paste
increases with the increase of curing time up to 90 days; this
is due to the continuous hydration of C3S and b-C2S which lib-
erate free lime. On the other hand, the free lime contents of all
MK-pozzolanic cement pastes increase with increasing hydra-
tion time up to 7 days, then decrease up to 90 days. The initial
increase of free lime of pozzolanic cement pastes is mainly due
to its liberation during the hydration of OPC and then the
decrease after 7 days is due to its consumption by the MK.
There are two different processes, the first tending to increase
Ca(OH)2 content and the other tending to decrease it. At early
ages of hydration the rate of liberation of CH by OPC cement
pastes exceeds the rate of consumption by aluminosilicate
materials of MK; therefore, the CH content increases up to
7 days. After 7 days up to 90 days the rate of liberation of
CH by OPC cement pastes is less than the rate of CH con-
sumption by MK and thereby, the CH content decreases. Also,
the CH contents of all OPC–MK cement pastes are less than
those of OPC at all hydration ages due to the decrease of the
amounts of OPC minerals which are the source of CH. It is
clear that, the residual CH content of OPC–MK pozzolanic
cement pastes is mainly due to the pozzolanic activity of MK.
153
XRD analysis
8.5
8.0
Fig. 4 shows the XRD-patterns of hydrated OPC paste after
Free lime contents, %
7.5 curing for 3, 28 and 90 days. The patterns show that the
7.0 remaining parts of clinker minerals, namely b-C2S and C3S,
are still existing up to 90 days of hydration. This is indicated
6.5
by the decrease of the relative intensities of their peaks with
6.0 increasing age of the hydration up to 90 days as a result of
5.5 hydration of OPC phases. Also, the peaks of portlandite
(CH) phase increase with the increase of curing time due to
5.0
the hydration of the silicate phases of OPC clinker with the
4.5 formation of CSH and liberation of CH. The carboaluminate
100
hydrates can be formed and increase with time. Calcium
carboaluminate is mainly formed by the reaction of atmo-
spheric CO2 with the CAH as a result of hydration of
MK-pozzolanic cement [28].
XRD patterns of hydrated cement pastes of M1 (5 wt%
MK) cured at 3, 28 and 90 days are shown in Fig. 5. The pat-
terns show that anhydrous phases of clinker minerals b-C2S
and C3S are still existing up to 90 days; their peak intensities
decrease with curing time up to 90 days. Also, the intensities
of the peaks of portlandite increase with increase of curing
time due to the hydration of these silicate minerals with the
formation of CSH and liberation of portlandite.
Fig. 6 illustrates the XRD-patterns of OPC and OPC–MK
pastes containing 5, 15 and 20 wt% of MK (M1, M3 and M4)
up to 28 days of hydration. The patterns show that the inten-
sities of portlandite peaks of OPC paste are higher than those
of set of Pozzolanic cement pastes due to the pozzolanic reac-
tion of MK with CH. The intensity of calcite (CaCO3) peak
decreases with increasing MK contents; this is an indication
for the consumption of CH by MK. The intensity of C3S
and b-C2S minerals decreases with the increase of curing age
due to the progress of hydration process. The peak character-
istic for CaCO3 is mainly overlapped with that of CSH gel. The
quartz peaks are still present in OPC–MK blended cement
pastes (M1, M3 and M4) due to its unhydraulic properties.
The peak intensity of CaCO3 decreases with curing time due
to the effect of CO2 in the presence of H2O to form
Ca(HCO3)2.
Thermal analysis
The most widely used thermal method of analysis is differen-
tial thermal analysis (DTA). Fig. 7 illustrates the DTA/DTG
thermograms of the hydrated OPC paste after curing up to
90 days. The DTA thermograms show the occurrence of four
endothermic peaks at 100, 150, 420–450, 700–750 C. The
endothermic peaks located below 200 C are mainly due to
the dehydration of interlayer water of CSH and CAH or
CASH, whereas the endothermic peak appeared at
420–450 C is due to the decomposition of Ca(OH)2 [26].
The last endothermic peak located at 700–750 C is due to
the decomposition of CaCO3 [27]. It is clear that the intensities
of the endothermic peaks characteristic for Ca(OH)2 and
CaCO3 increase with the increase of curing time up to 90 days
due to progress of hydration of OPC pastes. Also, the
endothermic peaks of CSH and CASH increase with curing
time due to progress of hydration.
154 H. El-Diadamony et al.

1= Portlandite 2= C3S 1 1
OPC - 3 days
3= B-C2S 4= Calcite OPC - 28 days
5= Cc OPC - 90 days

4 2+3
1
90 days 1
5
2+3

Intensity
4 2+3
28 days 1 1
1
2+3
1
5

2+3
4 1
3 days 1
2+3 1
1

10 20 30 40 50
2-Theta - Scale

Fig. 4 XRD-patterns of hardened OPC paste cured at 3, 28 and 90 days.

1= Portlandite 2= C3S 3 1 M1- 3 days

1 2 M1-28 days
3= B-C2S 4= Calcite M1-90 days
5= Cc 4
2 90 days
2
5 3
3 1
3
2
4
1
1
28 days
Intensity

2
5 1
2 3
3
3
4 1
2
1
3 days

2 1
2
3

10 20 30 40 50
2-Theta-Scale

Fig. 5 XRD patterns of OPC–MK pozzolanic cement pastes of M1 cured at 3, 28 and 90 days.

1= Portlandite 2= C3S 2 1 OPC - 28 days

3
1 M1- 28 days
3= B-C2S 4= Calcite
M3- 28 days
5= Cc 6= Quartz M4- 28 days
6 4
6 2+3 1
M4

4
6 1
2+3 1
M3 1
6
Intensity

4
1 1
5 1 2+3
M1

32

4 1
1 1
2+3
OPC 5

10 20 30 40 50
2-Theta-Scale

Fig. 6 XRD-patterns of OPC and hardened OPC–MK pozzolanic cement pastes of M1, M3 and M4 cured at 28 days.
Hydration and characteristics cement pastes 155

100
OPC 3 days 98
OPC 28 days
90 d (DTG) 96
OPC 90 days

Exo
28 d 94
3d
92

Weight loss, %
90
88

ΔT
86

3d 84
82
28 80
Endo

78
(DTA)
90 d 76
74

0 200 400 600 800 1000

Temperature,oC

Fig. 7 DTA/DTG thermograms of the hydrated OPC pastes cured to 90 days.

The hydration progress can be studied from thermal gravi-
metric analysis (TGA). The weight loss of the hydrated phases
without Ca(OH)2 and CaCO3 increases with curing time. The
weight loss increases with slow rate up to 3 days, followed by
higher rate up to 90 days. The TG losses characteristic for the
hydration products at low temperatures (up to 200 C) are
7.796%, 9.668% and 11.78% after 3, 28 and 90 days,
respectively. This means the degree hydration increases with
increasing time of curing. On the other hand, the TG losses
characteristic for CH are 4.451%, 5.718% and 6.804% after
3, 28 and 90 days, respectively. The increase of TG loss of
portlandite with curing time is due to the continuous liberation
of CH as a result of hydration of OPC. The TG losses due to
the decomposition of CaCO3 are 4.994%, 6.883% and 5.678%
after 3, 7 and 28 days, respectively. Also, the TG losses due to
CaCO3 decrease with curing time; this is attributed to the reac-
tion of CO2 and the moisture with CaCO3 with the formation
of Ca(HCO3)2.
The DTA/DTG thermograms of hydrated OPC–MK poz-
zolanic cement paste made of mix M1 and cured up to 90 days
are shown in Fig. 8. Evidently, there are four endothermic
peaks. The first endothermic peak located below 100 C is
mainly due to the removal of free water and the decomposition
of the amorphous part of calcium silicate hydrates (CSH). The
second endothermic peak observed at about 150–160 C repre-
sents the decomposition of crystalline part of CSH, CAH,
CASH as well as the presence of carboaluminate and gehlenite
hydrates [28]. The third endotherm located at about 450 C
represents the dehydration of calcium hydroxide (CH) [5,26].
The last endothermic peak located at 710–715 C is due to
decomposition of CaCO3 [26,27]. It is clear that the second
endothermic peak located at about 155 C increases with cur-
ing time due to the formation of excessive amounts of CAH
and CASH on the expense of CSH. These phases are formed
as a result of the pozzolanic reaction of MK with CH. The
main features of the thermograms are characterized by the rel-
ative increase of the peak areas characteristic for CH, CAH,
CASH and CSH phases as the hydration time increases up
to 90 days; this is due to that the small amount of MK acts
as nucleation agent which enhances the hydration process.
The endothermic peak located at 709–713 C is mainly due
to the decomposition of CaCO3.
The weight losses of hydrated phases up to 200 C are
8.248%, 11.650%, 10.620% for OPC–MK blend of mix M1
hydrated for 3, 28 and 90 days, respectively. The TG losses of
hydrated cement paste made of OPC–MK blend of composition

M1 3 days
M1 28 days 100
M1 90 days
98
96
Exo

94
(DTG)
Weight loss, %

92
3d
28 d 90
ΔT

90 d 88
3d 86
84
Endo

28 d 82
(DTA) 80
90 d 78
76

0 200 400 600 800 1000

Temperature, oC

Fig. 8 DTA/DTG thermograms of hydrated metakaolin pozzolanic cement pastes (M1) cured up to 90 days.
156
M1 are 4.846%, 5.884% and 7.165% for 3, 28 and 90 days,
respectively; these are due to the dehydration of portlandite.
This indicates that 5 wt% MK acts as nucleating agent which
accelerates the rate of hydration of OPC. The losses due to the
decomposition of CaCO3 are 4.465%, 5.188% and 5.553% for
cement pastes hydrated for 3, 28 and 90 days, respectively.
The TG losses of CaCO3 increase with curing time, and this is
due to the continuous carbonation of portlandite.
The DTA/DTG thermograms obtained for OPC and
OPC–MK mixes having MK contents of 5, 15, 20 wt%
(M1, M2 and M3) pozzolanic cement pastes cured for 28 days
are seen in Fig. 9. This figure shows the same four endothermic
peaks appeared in the thermograms obtained for the
OPC–MK made of M1. The peak areas appeared in the ther-
mograms obtained for OPC–MK pozzolanic cement pastes
having MK contents of 5–15%, by weight, are nearly identical
to those of the neat OPC pastes and then decrease at 20 wt%
MK substitution due to the dilution of OPC as well as the
pozzolanic reaction of MK with portlandite.
The TG losses of the CSH, CAH and CASH are 9.668%,
11.65%, 11.65% and 10.95%, respectively; this means that
substitution of 5–15 wt% MK acts as microfiller and nucleat-
ing agent which accelerates the rate of hydration and thereby
the combined water increases. This is in agreement with the
results of DTA. The weight loss of M1 cement paste due to
the dehydration of CH is higher than that of OPC, M3 and
M4. This indicates that 5 wt% MK acts as a nucleating agent.
On the other hand, the weight loss decreases with increasing
MK content due to the pozzolanic reaction of MK with CH.
The last step in the TG thermograms is the decomposition of
CaCO3; the TG losses are 4.49%, 5.044%, 5.183% and
6.883% for OPC and OPC–MK pozzolanic cement pastes
made with 5, 15 and 20 wt% MK. Therefore, the CaCO3 con-
tents increase with increasing MK content in the OPC–MK
pozzolanic cement pastes.
Bulk density
The bulk density of OPC and pozzolanic cement pastes
made of OPC substituted with 5, 10, 15 and 20 wt% MK are
Exo.
M4
ΔΤ
M1
M3
OPC
Endo.
------ DTA
0 200 400
Temperature,oC
Fig. 9 DTA/DTG thermograms of OPC and OPC–MK pozzolanic cement pastes (M1, M3 and M4) cured up to 28 days.
H. El-Diadamony et al.
graphically represented as a function of curing time in
Fig. 10. The bulk density of OPC–MK pozzolanic cement
pastes depends on the value of degree of hydration. As the
hydration progresses, the hydration products fill a part of
the pore volume because the volume of the hydration products
is more twice than that of the anhydrous cement; this increases
the bulk density of the hardened pastes [28]. The bulk density
of all cement pastes increases with curing time. As the amount
of MK increases the bulk density decreases. This is mainly due
to the increase of the amount of water of consistency with MK
content in addition to the decrease of specific gravity of MK
(2.65 g/cm3) in comparison with 3.15 g/cm3 of OPC (Table 1);
the initial water/cement ratio plays an important role in the
values of bulk density. This is also due to that the rate of
hydration of MK is lower than that of OPC especially at the
early ages of hydration. The values of bulk density of poz-
zolanic cement pastes are lower than those of OPC pastes, at
all curing times. In addition, the CSH formed from the poz-
zolana reaction has low density in comparison with that
formed from the hydration of OPC. Therefore, the pozzolana
cement pastes show lower values of bulk density [24].
Total porosity
The total porosity of OPC and OPC–MK pozzolanic cement
pastes is also graphically represented as a function of curing
time in Fig. 10. The porosity of the hardened pastes depends
on many factors and typically increases with increasing W/C
ratio and decreases with curing time; in addition, the type of
cement plays a certain role [29]. The paste has the highest
porosity immediately after mixing with water. As the hydra-
tion proceeds, the hydration products fill a part of the pore
volume, and accordingly the porosity decreases [30]. The total
porosity of OPC and OPC–MK pozzolanic cement pastes
decreases with curing time due to the continuous precipitation
of more hydration products within the pore system which leads
to decrease the porosity. As the MK content of the OPC–MK
mixture increases up to 20 wt% the total porosity values are
relatively high due to the increase of water of consistency of
OPC–MK blended cement pastes in addition to the relatively
100
OPC 28 days 98
M1 28 days
96
M3 28 days
M4 28 days 94
92
90
WEIGHT, %
88
86
84
82
80
78
76
DTG
74
72
70
600 800 1000
Hydration and characteristics cement pastes 157

2.19
OPC M1 M2 M3 M4
2.18 -------- Total porosity

2.17 Bulk density 22

2.16

Bulk density, g/cm3

Total porosity, %
2.15

2.14

2.13 20

2.12

2.11

2.10

2.09 18
1 10 100
Curing time, days

Fig. 10 Bulk density as well as total porosity of OPC and OPC–MK pozzolanic cement pastes up to 90 days.

low hydraulic character of MK in comparison with OPC. [32]. It is clear that the compressive strength of all cement pastes
Therefore, the change in total porosity of OPC–MK blended increases with increasing time of hydration up to 90 days. This
pastes depends not only on curing age, but also on the MK mainly due to the increase of the amount of hydration products
content. The total porosity is sharply decreased up to 7 days such as CSH, CAH and CASH and their later accumulation
and slightly decreased up to 90 days. This is due to the nucle- within the available pores giving high strength [33]. It is clear
ating agent of MK which accelerates the hydration and then also that pozzolanic cement paste having 5% MK gives the
the amount of hydration products increases and fills excessive highest compressive strength values than those of OPC or the
parts of the open pores at early ages of hydration [30,31]. other pozzolanic cement pastes. This is also due to that
It is clear that the OPC–MK paste containing 10 wt% MK 5 wt% MK acts as nucleating agent which accelerates the
gives apparent porosity values similar to those of OPC pastes. hydration of OPC. On the other hand, there is no real difference
of compressive strength of OPC and the other blended cement
Compressive strength pastes containing 10–20 wt% MK. As the MK increases up to
20 wt% the compressive strength is slightly decreased. This is
The compressive strength values of OPC and OPC–MK due to the dilution of OPC, which decreases the compressive
Pozzolanic cement pastes are graphically represented as a func- strength of pozzolanic cement pastes [34].
tion of curing time in Fig. 11. The effect of pozzolana (MK) on The increase of strength would be due to higher surface
the strength of OPC–MK pozzolanic cement pastes depends on area of MK resulting in more nucleation sites to improve reac-
a number of factors such as the pozzolana content of the tivity and improve packing as well as their pozzolanic reactiv-
cement, the type and surface area of pozzolana as well as the ity [35].
individual characteristics of the blending Portland cement
Conclusion

140
From the above finding it may be concluded that:
OPC
M1
M2 (1) Metakaolin fired at 850 C for two hours is mainly com-
120 M3 posed of quartz as a crystalline mineral in addition to
Compressive strength, MPa

M4
the amorphous aluminosilicate glassy phase.
(2) Substitution of 10 wt% OPC by MK increases the water
100 of consistency and then decreases up to 20 wt%. On the
other hand, the initial and final setting times are elon-
gated up to 10 wt% then shortened.
80 (3) The free lime contents of OPC–MK pozzolanic cement
pastes increase up to 7 days then decrease up to 90 days
due to the pozzolanic reaction of MK.
60 (4) The results of free lime of OPC–MK pozzolanic cement
decrease with increasing time of hydration.
1 10 100
(5) The results of XRD are in agreement with those of
Curing time, days DTA.
(6) The compressive strength values of OPC–MK
Fig. 11 Compressive strength of OPC and MK pozzolanic pozzolanic cement pastes containing up to 20 wt% have
cement pastes up to 90 days. small differences up to 90 days.
158 H. El-Diadamony et al.

[16] ASTM Designation: C191, Standard Method for Normal

Consistency and Setting of Hydraulic Cement, ASTM Annual
Conflict of interest
Book of ASTM Standards, 04,01, 2008.
[17] H. El-Didamony, A.A. Amer, H. Abdel-Aziz, Properties and
There is no conflict of interest. durability of alkali-activated slag pastes immersed in sea water,
Ceram. Int. 38 (2012) 3773–3780.
[18] H. El-Didamony, A.M. Sharara, I.M. Helmy, S. Abdel-Aleem,
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