Construction and Building Materials 34 (2012) 381384

Contents lists available at SciVerse ScienceDirect

Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Use of clay as a cement replacement in mortar and its chemical activation

to reduce the cost and emission of greenhouse gases
Noor-ul-Amin
Department of Chemistry, Abdul Wali Khan University, Mardan, Pakistan

a r t i c l e

i n f o

Article history:
Received 7 July 2011
Received in revised form 21 February 2012
Accepted 25 February 2012
Available online 5 April 2012
Keywords:
Mortar
Clay
Quicklime
Greenhouse gases
Cost of production

a b s t r a c t
The effect of industrially produced quicklime on the strength development and pozzolanic reaction rates
of Clay-Cementitious systems was investigated. The compressive strength development of mortars containing QuicklimeClayCement (CCL) was studied and presented. New efciency factors were calculated in order to nd out the optimum amount of quicklime to be added. The addition of quicklime
increased both the early and later strengths of the cementclay specimens. Hydration evolution and pozzolanic reaction rates of the QuicklimeClayCement (CCL) system were monitored. To know the
quantity of hydration products, Non-evaporable water content of the produced pastes was determined.
A 3% addition of quicklime was found as optimum dosage both for short and longer curing periods.
The increase in the strength could be due to the fact that the lime fully employed the available silica from
the clay to form additional cementitious compounds, prevailing pozzolanic calcium silicate hydrate with
increase in the amount of quicklime, no accelerating effect was detected due to the diminished proportion of soluble silica in the pore solution.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
The partial replacement of cement in mortar and concrete with
pozzolanic materials are aimed different reasons, including the
strength enhancement [1,2], improvement in durability [3], increased strength with age, good compaction, and to low heat evolution during hydration [4]. Its use greatly improves the water
tightness, lls in voids and act as ller to reduce the total surface
area to be covered with cement. Indeed, cement production is highly
energy intensive process involving signicant environmental damage with respect to CO2 production and raw material acquisition [5].
It is an acceptable fact that cement is a major construction
material through out the world [6]. Industrial wastes like blast furnace slag, coal y ash, silica fume and hazel nutshells are being
used as a supplementary cement replacement material. The agricultural waste like rice husk ash, wheat straw ash and clay are used
as pozzolanic materials [7]. When pozzolanic materials are added
to cement, the silica (SiO2) present in these materials reacts with
free lime released during the hydration of cement and forms additional calcium silicate hydrate (CSH) as new hydration products
[8,9] which improve the mechanical strength of the cement mortar
and concrete.
Several activation techniques have been adopted by numerous
researchers to deal with pozzolanic materials. The principal aim
Tel.: +92 938 331987.
E-mail address: noorulamin_xyz@yahoo.com
0950-0618/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2012.02.022

of these attempts was to enhance the reactivity of the pozzolan,

so as to improve the mechanical properties and durability of the nal product. Prolonged grinding [10], curing at elevated temperatures [11], and chemical activation [12] are some of the methods
that have been used to achieve the above mentioned properties.
However the efciency, of some of these methods is debatable,
since some are too energy demanding, while others fail to reasonably save the cost of the nal product.
Many studies have been carried out concerning the activation of
different pozzolanic materials by chemical methods [12]. It has
been investigated that the addition of hydrated lime accelerated
the reaction of clay both in the early and later ages. It is emphasized that this acceleration effect would be minimal unless curing
takes place at higher than room temperatures.
For dissolving the alumina and silica from the rm chain existing in the clay particles surface, a pH value of 13.3 or higher is required [13,14]. The fact that the pH of the system clay-calcium
hydroxide rarely exceeds 13 and the anticipation that lime and clay
interaction is quite complex and not very fast, led several workers
in the introduction of a third component in the mix [1517].
The objective of the present work is to evaluate clay as supplementary cementitious material and its activation by chemical
method using industrially produced quicklime. It has been emphasized through the work done that the clay could be used to replace
the cement up to a considerable extent. The aim to replace cement
by clay in mortar is to reduce the emission of greenhouse gases and
the cost of production of cement.

382

Noor-ul-Amin / Construction and Building Materials 34 (2012) 381384

2. Experimental
2.1. Materials
The cement used in this study was high strength Portland cement meeting the
Pakistan standard specication PS: 232-1983 (R) and its chemical composition of
cement used in this study is shown in Table 1 [18]. Commercial quicklime of high
purity was used as activator. The sand employed was 100% pass through 850 lm
and 10% pass through 600 lm sieve, according to Pakistan standard specication.
The clay was collected from cherat mines Khyber Pakhtoon Khwa, Pakistan. The
clay was ground to a blaine neness of 4000 cm2/g and was studied using X-ray
uorescence techniques. The mineralogical composition of the clay is given in Table 2 [19].

2.2. Procedure
2.2.1. Addition of quicklime and formation of new blends
In order to incapacitate the effect of neness on the performance of clay, the
raw clay was ground in a lab mill before use, so as to obtain clay of uniform neness. The particle size distribution of the ground clay indicates the absence of any
signicant differences in their nal granulometry as shown in Fig. 1. A corresponding amount of clay was replaced in the mix by the addition of specic amount of
quick lime. The activated blends were named according to the quantity of quick
lime added, i.e. CC3L and CC6L corresponds to the specimens containing 3%
and 6% quick lime respectively. A blend containing no quick lime was named as
CC0L, and one with out quick lime and clay as control.

2.2.2. Thermal analysis and determination of free calcium hydroxide in the hardened
pastes
The extent of pozzolanic reaction in the blend can be estimated by determining
the amount of unbound calcium hydroxide (CH) in the hardened paste. TG and DTA
were used to determine the amount of unbound CH in the hardened paste at the
testing ages and thus the progress of pozzolanic reaction was monitored. The measurements were performed by a Mettler STARe 851/LF/1600 TG/SDTA instrument. A
Platinum crucible with 70 ml capacity was used and mass of the examined samples
ranged from 45 to 55 mg. The samples were tested in nitrogen atmosphere
(50 mL min1) at a heating rate of 10 C min1 from ambient temperature to
1000 C. The weight of calcium hydroxide in the samples (indicated by the abrupt
weight loss occurring in the temperature region of 400550 C) and the quantity
of free-Portlandite transformed into calcium carbonate (due to atmospheric carbonation) were estimated and afterwards added to determine the total CH percentage
in all specimens.

2.2.3. Non-evaporable water contents

To determine the non-evaporable water content (Wn) of the hydrated samples,
1 g of the hydrated sample was rst dried at 70 C for overnight (dried weight of
paste) and was afterwards ignited at 950 C in an electric furnace for 1 h and Wn
content of the samples was calculated using the following equation [5]:

Wn

W1  W2
r fc

W2
1  r fc

where, Wn is the non-evaporable water content; W1, the weight of specimen before
ignition; W2, the weight of specimen after ignition; rfc is the coefcient taking into
account the loss on ignition and weights of the cement and clay used in each blend
as under;The coefcient is calculated as follows:

rfc pf rf pc rc

where, pf is the weight percentage of clay; pc, the weight percentage of cement; rf,
the loss on ignition of clay; rc is the loss on ignition of cement.
Obviously in the present study, where the clayquicklime blends substituted
20% (by weight) cement in all the pastes, pf = 0.2 and pc = 0.8.

Table 1
Non-evaporable water contents of cement, cement clay and quick lime activated
claycement pastes.
Material

Control
CC0L
CC3L
CC6L

Wn contents (%)
3 days

7 days

28 days

10.63
9.21
10.69
10.87

11.09
12.52
12.57
12.34

15.31
14.87
16.57
15.19

2.2.4. Determination of compressive strength

For studying the effect of compressive strength of the blend mortar, mixes were
prepared by adopting a cementitious to sand ratio of 1:3 by mass. Blended cement
containing clay was mixed with water in water to cement ratio of 0.45 (v/w). The
obtained blends were used to substitute 20% (by weight) cement in all mortars.
For every blend, three molds were made for triplicate reading and the mean value
has been reported. Keeping the w/b ratio constant, a cement mortar without any
clay or quicklime was prepared as the control and one with clay but without lime
(CC0L). The blends were sufciently mixed in dry and wet condition for four minutes, and were cast into mold of 40 mm  40 mm  40 mm using a vibrating machine with a normal speed of 1200 rpm for 120 s in order to get compact cubes.
The ambient temperature for the mixing was kept at 20 2 C and relative humidity
of 65%. The molded samples were placed in the moist curing chamber for 24 h at a
temperature of 20 1 C and relative humidity of 90%. After 24 h, the specimens
were stripped from their molds and were placed in water curing tank having a temperature of 20 1 C until testing. A Toni tecknik compressive strength machine
with a load cell of 0300 kN and a loading rate of 2.4 kN/s was used for the compressive strength. The compressive strength of the specimens was measured
according to British standard specications BS 196-1 and Pakistan standard specication PS 232-1983 (R), after 3, 7 and 28 day from the mixing date. The corresponding pastes were prepared using a similar procedure, adopting the same
water to binder (w/b) ratio and curing under water, in order to monitor the hydration process of the claycementquicklime systems. For each age, three specimens
of every mixture were tested and the mean value of these measurements was
reported.

2.3. Efciency factors

The concept of the efciency factor or simpler k-value has been introduced as a
way to predict the effect of clay on the compressive strength of Portland cement
systems. In other words, the efciency factor is dened as the part of the clay, which
can be considered as equivalent to high strength Portland cement, having the same
properties as the mortar without clay (obviously k = 1 for Portland cement) [20]. In
this work, the efciency factors were determined in order to draw conclusions
regarding the effectiveness of each activation dosage applied.

3. Results and discussion

3.1. CH contents and pozzolanic action ratio
The percentage of the unreacted CH in the pastes during the
examined hydration ages was determined in order to investigate
the pozzolanic reaction rate of the activated systems. The CH contents of the claycement with different hydration ages are shown
in Fig. 2. It can be seen that the cement paste without any clay substitution (control mixture) is constantly producing CH throughout
the hydration period. On the contrary, the peculiar image that the
specimens with clay exhibit can be explained by the simultaneous
production and consumption of calcium hydroxide. In the frame of
this work, the erratic behavior of the examined samples can be
attributed to the fact that there are three sources of calcium
hydroxide production inside the matrix. Apart from the cement
grains that react instantly, free lime present in clay and the added
quicklime is hydrated to provide an excess of CH in the matrix of
the activated systems.
It can also be observed from the gure, that a small clay replacement by lime (3%) accelerated the CH depletion from the early period of hardening. This effect is more prominent after the rst
3 days, where less CH is present in the paste after the rst week
of hydration, inspite of the fact that the activated blend contains
initially more lime than the corresponding claycement system.
It is obvious that the addition of 3% quicklime accelerates the consumption of Ca(OH)2 as the hydration proceeds greater quantities
of Ca(OH)2 measured after 28 days indicate the inability of its
low active silica content to bind signicant quantities of lime. On
the other hand, although the blend with 3% of lime lacks pozzolan,
and more Ca(OH)2 is combined. This is obviously the outcome of
the activation of the glass constituents of the clay, due to the formation of a higher alkalinity environment. The addition of lime
led to the corrosion of the chemically stable surface layer of the
clay allowing more active centers to run freely in the pore solution

383

Noor-ul-Amin / Construction and Building Materials 34 (2012) 381384

Table 2
Chemical composition of high strength Portland cement.
Major elemental oxides (wt.%)
SiO2
21.55

Al2O3
5.69

Moduli

Fe2O3
3.39

CaO
64.25

MgO
0.85

MA
1.68

120

80
60
40
20
0
1

12

16

24

32

48

64

96

Diameter (micrometer)
Fig. 1. Particle size distribution of ground clay.

25

3 days

7days

28 days

20

CH-contents

15

LSF
0.93

C3S
47.61

C2S
25.90

C3A
9.35

C4AF
10.30

with hydration age. This is the outcome of progress of the hydration and the continuing accumulation of hydration products. The
addition of quicklime increased notably the amount of combined
water of high-calcium claycement pastes at all ages. It can be seen
that during the examined period of hydration, the non-evaporable
water contents of all the activated pastes with high calcium clays,
is higher than that in the paste built with plain cement. In any case
of addition and for all hydration stages, the unitary Wn contents are
signicantly higher than in the Cement pastes. It seems that apart
from the contribution of the clay pozzolanic reaction and the enhanced hydration due to the higher effective w/c ratio, the presence of quicklime accelerated the rate of formation of hydration
products. According to Shi [4], when quicklime contacts water, it
hydrates rapidly liberating much heat. The liberated heat can also
accelerate the pozzolanic reaction between the clay and CH contained in the matrix, leading to a higher pozzolanic reaction rate.
This rapid acceleration could also be responsible for the higher
Wn contents observed in clayquicklimecement pastes, from the
very early stages of hydration.
3.3. Compressive strength

10

0
Control

C-C-0L

C-C-3L

C-C-6L

Mix proportion
Fig. 2. CH contents of the cement, cementclay, and quicklime-activated clay
mortars.

and participate in the pozzolanic reactions. This fact accounts for

the improved strength observed in lime-activated specimens. Increased quicklime addition (6%) slightly increased uncombined
CH inside the matrix. Especially noticeable is the fact that from
the rst week onwards, the blend with 6% quicklime seems to bind
greater quantities of calcium hydroxide, completely consuming the
extra 3% of quicklime added.

3.2. Non-evaporable water contents (Wn)

Non-evaporable water content of the constructed pastes was
determined in order to investigate the quantity of the formed
hydration products in each case. Despite the fact that the amount
of water retained in the products of hydration cannot be completely associated with the degree of complex pozzolanic reactions,
it can indicate the effectiveness of quicklime in activating the
examined systems and the role of each dosage applied. The data
for the combined water contents of all specimens as a function of
curing time is shown in Table 3. It is obvious that for all hardened
pastes, the chemically combined water content increases gradually
Table 3
Mineralogical composition of clay.

Al2O3
28.7

Fe2O3
2.8

The compressive strength results of all the produced systems

plotted against hydration time are shown in Fig. 3. From the gure
it is obvious that both the 3% and 6% clay replacement with quicklime slightly enhanced the compressive strength of the initial clay
mortar, from the early period of hardening. However, the control
out performed all clay mortars (with or without activator) during
the rst week of hydration. It seems that the addition of lime in
the matrix cannot compensate for the cement loss at this stage.
From the rst week onwards, the clay specimens are approaching
the value of the control and even exceed it (at 28 days), as a result
of the evolution of their pozzolanic action. When clay replacement
by quicklime was increased to 6%, the strength of the activated
mortar was found higher than that of the control specimen at all
ages, but slightly diminished compared to the values obtained with
less lime addition. This is an indication that addition of lime must
be limited to 3% only. From the above discussion, it can be concluded that the 3% lime is the optimum content both for short
and longer curing periods. It is possible that a small dosage of lime
fully employed the available amorphous silica from the clay to form
additional cementitious compounds, prevailing pozzolanic CSH.
It has been observed [21,23], that in the presence of Ca(OH)2, the

3 days
28 days

60

7 days

50
40
30
20
10
0

Major elemental oxides (wt.%)

SiO2
58.4

MS
2.37

Compressive strength N/mm2

Weight (%)

100

Cement potential

Control

CaO
0.28

MgO
0.3

Na2O
0.2

K2O
0.2

C-C-0L

C-C-3L

C-C-6L

Mix proportion
Fig. 3. Compressive strength of the quicklime-activated clay mortars.

384

Noor-ul-Amin / Construction and Building Materials 34 (2012) 381384

3 days

1.2

7 days

cost of cement mortar and consequently the emission of greenhouse gases to a considerable extent. Addition of quicklime in
claycement systems is an effective, relatively cheap and environmental friendly way to accelerate the degree of clay reaction. Since,
in this work quicklime actually replaced clay and was not additionally added in the mix, the loss of active silica due to clay replacement, was critical in the nal performance of the newly
constructed activated blends.

28 days

k. value

1
0.8
0.6
0.4
0.2

References

0
Control

C-C-0L

C-C-3L

Mix proportion
Fig. 4. Efciency factors (k-values) for cementclay and cement-activated clay
mortars.

solubility of SiO2 increases notably, indicates that as the hydration

progresses, greater quantities of soluble silica are released from the
reacted clay particles into the matrix [23]. This accounts for the improved strengths of activated clay observed at later ages. During the
early stages of hydration, added lime works alternatively to enhance the strength of the system. Addition of quick lime and its subsequent conversion to Ca(OH)2, results in a higher basicity inside
the matrix. The increase in pH leads to the corrosion of the densied
outer layer of clay particles [24], leaving more active cores exposed
for reaction that form additional hydration products. Another way
to explain the improved early age strengths observed in lime-activated clay systems is the formation of ocs inside the matrix due to
lime hydration. It has been observed [25] that these ocs reduce the
effective voids, and hence the interconnectivity of the pores, leading to a denser microstructure.
3.4. Efciency factors
The method described by Palomo et al. [26] was followed for
estimating the k-values. Briey, in the case of mortars and concrete
that incorporate supplementary cementing materials, the k-value
derives from the following expression for the compressive strength
(fc) measured for the formed systems:

fc K

1
W=C kP

where, K is a parameter depending on the cement type (here

38.8 MPa); C, the cement contents in the mortar (kg/m3); P, the clay
contents in the mortar (kg/m3); W is the water content (kg/m3).
In this work done, where a small amount of clay has been replaced by quicklime, P is considered as the sum of clay and quicklime in each blend. Using the measured values of the compressive
strength, the k-values for the activated systems were calculated by
means of the above equation and the results are shown in Fig. 4.
The k-values are below unity during the early ages and then exceed unity, as the hydration progresses. This means that up to a
certain level, the clay substitutes for cement. For a similar pozzolan
addition (20% by weight of cement), all the samples with clay have
a k-value less than 1 at 3 days, but afterwards as the clay is involved in the pozzolanic reactions, the k-values reaches unity.
4. Conclusion
Addition of clay in cement mortar and its chemical activation
replaced equal amount of cement in mortar which decreased the

[1] Shi C, Day RL. Pozzolanic reaction in the presence of chemical activators. Part I:
reaction kinetics. Cem Concr Res 2000;30:518.
[2] Antiohos SK, Papageorgiou A, Papadakis VG, Tsimas S. Inuence of quicklime
addition on the mechanical properties and hydration degree of blended
cements containing different y ashes. Constr Build Mater 2008;22:1191200.
[3] Bentur A. Cementitious materials nine millennia and a new century: past,
present, and future. ASCE J Mater Civil Eng 2002;14:222.
[4] Demirbas A, Asia A. Effect of ground hazel nutshell, wood and tea waste on the
mechanical properties of cement. Cem Concr Res 1998;28:11014.
[5] Antiohos SK, Papadakis VG, Chaniotakis E, Tsimas S. Improving the
performance of ternary blended cements by mixing different types of y
ashes. Cem Concr Res 2007;37:87785.
[6] Janotka I, Mojumdar SC. Degree of hydration in cement paste and C3Asodium
carbonatewater systems. J Therm Anal Calorim 2007;90:64552.
[7] Ismat A. Biomass: an ideal fuel for sugar mills for steam/power generation, vol.
197. PCSIR (Karachi): Fuel research centre; 2004. p. 1220.
[8] Xie Z, Xi Y. Hardening mechanisms of an alkaline-activated class F y ash. Cem
Concr Res 2001;31:12459.
[9] Poon CS, Kou SC, Lam L, Lin ZS. Activation of y ash/cement systems using
calcium sulfate anhydrite (CaSO4). Cem Concr Res 2001;31:87381.
[10] Mira P, Papadakis VG, Tsimas S. Effect of lime putty addition on structural and
durability properties of concrete. Cem Concr Res 2002;32:6839.
[11] Chakchouk A, Samet BB, Mnif T. Study on the potential use of Tunisian clay as
pozzolanic material. Appl Clay Sci 2006;33:7988.
[12] Amin N, Ali K, Shah MT, Alam S. Chemical activation of bagasse ash in cement
mortar. Adv Cem Res 2011;23:8995.
[13] Amin N. Use of clay as a pozzolona in high strength Portland cement and its
thermal activation. Chin J Geochem 2010;29:1435.
[14] Amin N, Shah MT, Ali K. Investigation of raw material for the manufacturing of
sulfate resisting cement in Darukhula Nizampur NWFP Pakistan. Mag Concr
Res 2009;61:77985.
[15] McLellan Benjamin C, Williams Ross P, Lay Janine, van Riessen Arie, Corder
Glen D. Costs and carbon emissions for geopolymer pastes in comparison to
ordinary Portland cement. J Clean Product 2011;19:108090.
[16] Huntzinger DN, Eatmon TD. A life-cycle assessment of Portland cement
manufacturing: comparing the traditional process with alternative
technologies. J Clean Product 2009;17(7):66875.
[17] Chen C, Habert G, Bouzidi Y, Jullien A. Environmental impact of cement
production: detail of the different processes and cement plant variability
evaluation. J Clean Product 2010;18(5):47885.
[18] Bouzouba N, Zhang MN, Malhotra VM. Chemical activators. Part II: reaction
mechanisms. Cem Concr Res 2000;25:2536.
[19] Amin N. Use of bagasse ash in cement and its impact on the mechanical
behavior and chloride resistivity of mortar. Adv Cem Res 2011;33:7580.
[20] Biricik H, Akoz F, Berktay I, Tulgar AN. Study of pozzolanic properties of wheat
straw ash. Cem Concr Res 1999;5:63743.
[21] Ali K, Amin N, Shah MT. Physicochemical study of bagasse and bagasse ash
from the sugar industries of NWFP Pakistan and its recycling in cement
manufacturing. J Chem Soc Pak 2009;31:3758.
[22] Guo X, Shi H, Dick WA. Compressive strength and microstructural
characteristics of class C y ash geopolymer. Cem Concr Compos 2010;
32:1427.
[23] Aaron RS, Anderson E, Schauer C, Barsoum MW. Mechanical and
microstructural characterization of an alkali-activated slag/limestone ne
aggregate concrete. Constr Build Mater 2009;23:29517.
[24] Chen JH, Huang JS, Chang Chang YW. A preliminary study of reservoir sludge as
a raw material of inorganic polymers. Constr Build Mater 2009;23:32649.
[25] Amin N, Ali K, Shah MT. Recycling of Bagasse ash in cement manufacturing and
its impact on clinker potential and environmental pollution. J Chem Soc Pak
2009;31:35761.
[26] Palomo A, Grutzeck MW, Blanco MT. Alkali-activated y ashes, cement for the
future. Cem Concr Res 1999;8:13239.