International Journal of Civil Engineering and Technology (IJCIET)

Volume 8, Issue 4, April 2017, pp. 2157–2172, Article ID: IJCIET_08_04_245

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ISSN Print: 0976-6308 and ISSN Online: 0976-6316

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IMPACT OF METAKAOLIN ON CEMENT

MORTAR AND CONCRETE: A REVIEW
K.Z. Farhan, W.A. Gul
Department of Civil Engineering, College of Engineering,
King Abdulaziz University, Jeddah, KSA

ABSTRACT
Concrete is unarguably the most extensively used construction material in the
world and this unprecedented use has resulted in serious environmental concerns
both in terms damage caused by the extraction of raw material and CO2 emission
during cement manufacture. The production of one ton of cement generates
approximately one ton of CO2 and requires huge amount of electrical power and fuel
energy. The solution has by far been the utilization of Supplementary cementing
materials (SCMs) which could, not only reduce the use of cement but also, equal or
increase the overall performance of the concrete. One such material that has been
extensively used as calcined clay is Metakaolin (MK), a pozzolanic material, which is
obtained by calcinations of kaolinitic clay. This paper reviews the overall work
carried out on the use of MK as partial replacement of cement in mortar and
concrete. A detailed literature survey is carried out and presented here.
Key words: Metakaolin, Pozzolan, Supplementary cementing materials, Cement,
Concrete.
Cite this Article: K.Z. Farhan and W.A. Gul, Impact of Metakaolin on Cement
Mortar and Concrete: A Review. International Journal of Civil Engineering and
Technology, 8(4), 2017, pp. 2157–2172.
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1. INTRODUCTION
The use of pozzolanas for making mortar or concrete is considered efficient, as it allows the
reduction of the cement consumption while improving the strength and durability properties
of the concrete. MK, sometimes also referred as “high-reactive metakaolin”, has 99.9 %
particles less than 16 µm with a mean particle size of about 3 µm an order of magnitude smaller
than cement grains and an order of magnitude larger than silica fume particles. MK typically
contains 50 to 55 % Sio2 and 40 to 45 % Al2 O3. Other oxides present in small amount
include Fe2o3, TiO2, CaO and MgO [52][49].

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 K.Z. Farhan and W.A. Gul

Table 1 Physical characteristics of selected pozzolans (Mindess et al., 2003) [32].

Material Mean Size (10-6 m) Surface Area (m2/g) Particle Shape Specific Gravity

Portland Cement 10-15 <1 angular, irregular 3.2

Fly Ash 10-15 1-2 mostly spherical 2.2-2.4

Silica Fume 0.1-0.3 15-25 spherical 2.2

Metakaolin (MK) 1-2 15 platey 2.4

Generally, the SCM’s with higher alumina contents, such as MK, tend to have higher
pozzolanic capacities because formation of C-A-H has a high CH demand. This is critical as
CH does not make a significant contribution to concrete strength and can be detrimental to
durability [52 ][49].

2. METAKAOLIN REACTIVITY
The calcinations conditions of kaolinite and characterization of MK has been subject of
extensive research and it has been established that the thermal activation of MK by
dehydration leads to break down or partial breakdown of structure and formation of a
transitional phase with high reactivity [2]. The principal reaction between AS2 and CH is
derived from cement hydration in presence of water. This reaction forms additional
cementatious C-S-H gel, together with crystalline products, which include calcium aluminate
hydrates and alum osilicate hydrates (C2ASH8, C4AH13 and C3AH6). The crystalline products
depend principally on the AS2/CH ratio and reaction temperature [38][57][29].

Table 2 Chemical composition of MK (Ambroise et al,1994)[2]

Compounds % by mass

SiO2 51.52
Al2O3 40.18
Fe2O3 1.23
CaO 2.0
MgO 0.12
K2O 0.53
SO2 0.0
TiO2 2.27
Na2O 0.08
LOI 2.01

In concrete, the presence of CH becomes a crucial performance indicator in a sense that,

when Portland cement alone hydrates, typically 20 to 30 % of resulting paste mass is CH,
however when MK is introduced as partial replacement, it is found to drastically impact the
CH concentration. Considerable research in this regard has been carried out; Kostuch et
al.(1993) reported a significant reduction of CH for all replacement level up to 20% and
replacement of 20% of cement for fully removing all the CH in concrete at 28 days[30].
Ambroise et al. (1994) showed that during the hydration period, CH was quickly consumed,
the microstructure was rich in CSH and stratlingite (C2ASH8), and the pore size distribution
was displaced toward smaller values at up to 30% replacement of MK[2]. Interestingly, Oriol

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 Impact of Metakaolin on Cement Mortar and Concrete: A Review

and Pera (1995) reported an increased replacement level of MK 30 to 40% for complete CH
removal from MK-PC paste at a water-binder ratio of 0.5 when cured in lime-saturated water
for 28 days[41].
Wild and Khatib (1997) measured CH consumption in MK-PC pastes and mortars, cured
in water at 20 °C. Results showed that the CH, expressed as a percentage of cement weight,
showed a minimum at about 14 days of curing. This was attributed to a peak in pozzolanic
activity for which more CH was being removed from the paste by reaction with MK than was
being generated by the cement hydration. Interestingly, the peak in relative compressive
strength (the ratio of strengths MK-PC to that of the control at the same age) coincided with
the maximum in pozzolanic activity at 14 days of age. Increases in CH content and a lag in
strength gain beyond 14 days were attributed to the formation of an inhibiting layer of
reaction product on the surface of the MK particles [55]. Similar results were established by
Poon et al. ( 2001) while determining total CH content of paste samples, both based on the
ignited weight and the weight of cement, using differential scanning calorimetry. Cement
blended with 20% MK showed the least CH at all ages and mixtures showed steadily
decreasing CH contents up to 90 days. Further, the degree of pozzolanic reaction of MK was
found to be higher at a 5% replacement level than 10 and 20%. The higher rate of pozzolanic
reaction in cement pastes with a lower replacement level was attributed to the higher
concentration of CH [43].

Figure 1 CH content calculated based on cement weight (Poon et al., 2001)[43]

Frías and Cabrera (2000) determined the degree of hydration of partially replaced (up to
25%) MK-OPC pastes from the total amount of calcium present in the hydrated MK/OPC
systems. Calcium hydroxide contents of MK/OPC samples increased with age until 3±7 days
and subsequently, the values start decreasing, more or less depending on MK content. In the
cases of mixtures with 10 and 15% of MK, an inflexion point at 56 and 90 days, respectively
was observed. Beyond this point, the calcium hydroxide content progressively increased. The
influence of calcium hydroxide content was attributed to different hydration mechanisms, the
increase in the Ca(OH)2 amounts were due to the OPC hydration, while the decrease in the
values were related to the pozzolanic reaction of MK. The inflexion points (for 10% and 15%
of MK) represent the end of the pozzolanic reaction, due to the total consumption of MK[20].

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 K.Z. Farhan and W.A. Gul

Figure 2 Evolution of CH with hydration time (Frías and Cabrera, 2000)[20].

3. EARLY AGE PROPERTIES

3.1. Workability & Setting Time
MK has been found to produce smaller slump than control mixtures, many researches have
been undertaken to understand the reasons for its water demand & influence on the flow
properties of concrete. Kinuthia et al.(2000) investigated the workability of concrete
incorporating combinations of pulverized fuel ash (PFA) and Metakaolin (MK) as partial
replacements for Portland cement (PC). The results showed that workability of PC-MK
concrete substantially reduced with an increase in MK content[29].
Similar researches undertaken by Wild et al., (1996), Rols et al.(1999) Bai et al.(1999),
Khatib and Clay (2003) Qian and Li (2001) showed that workability reduced substantially
for mixtures containing MK and required increased quantity of super plasticizer with
increase in MK content to compensate for losses in workability[56][47][8][25][45]. In
addition to that Luc et al. (2003) found that 10% to 15% replacement of cement by MK lead
to low decrease of workability and best mechanical performance[34].
More or less all the researches attribute workability reduction caused by MK to its high
chemical activity and high specific surface area, resulting in increased intake and hence
greater water requirement. The influence of MK on compaction and flow is attributed to the
thixotropic nature of clay suspension and to the reduction of void space due to improved
dispersal of the MK particles.
Comparing SCMs, Ding and Li (2002) found, MK offering much better workability than
SF[18]. Similar observation was made by Dubey & Banthia (1998) in their study of eight
mixes wherein they found that the reduction in workability due to replacement with 10%
silica fume was more pronounced than that obtained with replacement of MK of equal
amount. In both cases the author attributed the results to larger particle size of MK relative to
silica fume (1.5 µm v 0.1 µm)[19]. Calderone et al.(1994) observed that although the slump of
concrete containing 10% MK was reduced from that of concrete with PC only, the MK
concrete required 25%-35% less high range water reducers (HRWR) than equivalent SF
mixtures. This reduction in HRWR demand resulted in the MK having less sticky consistency
and better finish than SF concrete [49].

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 Impact of Metakaolin on Cement Mortar and Concrete: A Review

As far as setting time is concerned generally all SCM’s should delay the setting time
because they are never as hydraulic as Portland cement and hence in the first few hours there
would be a smaller percentage of active binder [49]. Brooks et al. (2000) examined the
effect of silica fume, MK, FA, and slag on setting time of high strength
concrete. Results reveal that all SCMs tend to retard setting time, and
that increasing the levels of SF, FA, and slag resulted in greater
retardation of the set. For HSC containing MK, there was a progressive
increase in the retarding effect up to 10% replacement, but a gradual
decrease was observed at higher replacement levels [13]. Similar results
were reported by Batis et al. (2004), who examined two types of MK product.
The author found all MK mixtures to have significantly longer setting times
than control pastes, but retarding effect decreases with increase in higher
replacement levels [10]. However in contrary Vu et al. (2001) reported that for
Vietnamese kaolin used in the study, setting times of pastes in the lower
replacement range (10-20% MK) were not significantly affected by blending.
Beyond this range, the initial and final setting times increased by 15% and
10%, respectively, likely due to the lower cement and higher water contents
involved[54]. Also in a similar contrast, Caldarone et al. (1994) and
Moulin et al. (Moulin, 2001) both found pastes made from MK blended cements
to have a much shorter setting time compared to control pastes. It was
found that the presence of MK significantly increased both the 5 and 90
minute yield stress when compared to reference pastes. Thus confirming that
MK blending results in a higher water demand and leads to thixotropic
behavior, which was attributed to the accelerating effect of MK on PC
hydration[14].

3.2. Alkali-Silica Reaction (ASR)

Alkali-silica reaction occurs between alkalis contained in cement paste and certain forms of
reactive silica within the aggregate. The mechanism of ASR is relatively complex, beginning
with de-polymerization, dissolution, re-polymerization of an alkali-silica gel product, and
swelling of the gel in the presence of water. If a sufficient amount of water is present, the gel
volume can increase, generating local tensile stresses in the concrete and eventually leading
to cracking, which can increase the permeability (furthering the reaction) and decrease the
strength and stiffness of the concrete. MK replacement can theoretically mitigate ASR
damage in 3 ways, by reacting with the extra CH, taking up alkalis to reduce the pH of the
pore solution and by decreasing the permeability of the concrete to reduce water infiltration
and hence control the expansion from ASR [46][52].
Secondary reactions involving SCMs promote refinement and densification of the
concrete microstructure, reducing permeability and limiting the availability of water. In
addition, when SCMs are used as partial replacement for cement, their effect is to dilute the
cement, which reduces the alkali content of the concrete system and the pH of the pore
solution, thereby increasing the solubility of calcium and promoting the formation of non-
expanding gel in place of swelling N(K)-S-H. Recent studies involving MK have indicated
that replacement levels of 10-15% should be effective in mitigating ASR[46][49][52].
Ramlochan et al. (2000)examined a MK from Georgia that was water-processed to
remove impurities. Concrete prisms contained either of two reactive coarse aggregates,

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 K.Z. Farhan and W.A. Gul

reactive sand, cement, and 0-20% SCM. Three Type I cements with varying alkali contents
were used. For all combinations of aggregate and cement, 15% MK was sufficient to suppress
ASR expansion to within the specified limit criteria. Author suggested that the mechanism by
which MK may suppress ASR expansion is entrapment of alkalis by the supplementary
hydrates and a consequent decrease in the pH of the pore solution. This was supported by
sampling pore solutions of paste samples over a two-year period and titrating to determine
OH- concentration[46].
Further Aquino et al.(2001) in its study of influence of two mineral
admixtures, silica fume (SF) and high-reactivity metakaolin (HRM) found that HRM and SF
significantly reduce expansion due to ASR. In addition, X-ray microanalysis showed that
calcium content increases with time in ASR products. Furthermore, it was found that as ASR
proceeded the calcium content of reaction products increased proportionally as the silica
content decreased [4].

3.3. Heat of Hydration

In most of the researches, the use of MK has been found to increase the heat evolution during
hydration. This has been attributed both to the accelerating effect of MK on PC hydration and
the high reactivity of MK with CH. Even though enhanced temperature rise becomes critical
in larger members and slabs, as it may lead to thermal stress cracking, the property is very
much desirable in cold weather concreting where faster set is required[49][52].
According to Zhang and Malhotra (1995), 10% MK as replacement with cement caused a
7 °C increase over PC-concrete [58]. Similarly, Ambroise et al. (1994) reported temperature
rise of 8 °C, 6 °C, and 1 °C over controls, for 10%, 20%, and 30% replacement, respectively,
in mortars. so the increase in temperature decreases with the increase in replament levels og
MK. The temperature increases at higher replacement levels are likely due to the dilution
effect of removing such a large mass of cement from the system. In comparison, replacement
with 10% silica fume produced a temperature rise of only 0.5 °C [2].
Frías et al. (2000) compared FA, silica fume, and MK in terms of heat evolution using a
Langavant calorimeter MK mortars produced a slight heating increase when compared to a
100% Portland cement mortar, due to the high pozzolanic activity of MK. With respect to the
hydration heat, MK-blended mortar showed closer behavior to SF than to FA. After 2 h, both
the SF and MK showed pozzolanic activity, while the FA, due to its lesser activity at early
stages, hardly showed any reaction with lime before day 28 [21].
Bai and Wild (2002) researched the effects of FA and MK on heat evolved using
embedded thermocouples. With increasing replacement levels, the temperature rise in FA
systems was found to decrease, while the temperature rise in MK systems was found to
increase substantially [7]. Numeric peak temperature values were as follows: 29 °C, 27 °C,
and 31 °C for the control, 10% FA, and 10% MK mixtures, respectively. Bai et al.(2003)
further investigated the use of FA and MK in ternary blends at total PC replacement levels of
up to 40%. These appeared to have a compensatory effect on temperature rise: the
temperature rise for a 10% FA-10% MK blend was exactly the same as that of the control [9].

4. PERMEABILITY & PORE SIZE DISTRIBUTION

The pore size distribution and permeability plays an important role in the performance and
durability of concrete and are largely dependent on particle size, chemical composition,
mineralogy and loss on ignition of added pozzolans [52]. Frias and Carbrera (2000)
investigated the evolution of capillary and gel porosity with hydration time by Mercury
Intrusion Porosimetry (MIP) wherein capillary pores were considered to fall within 0.01-5.00
µm, while gel pores were smaller than 0.01 µm. Results revealed a reduction in total porosity

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 Impact of Metakaolin on Cement Mortar and Concrete: A Review

observed up to 28 days after which it remained more or less constant. Mixtures containing
MK actually showed higher total porosities than controls (approximately 16%), likely due to
the high water content, although the MK pastes had fewer pores in the 0.01-5.00 µm range
and more pores smaller than 0.01 µm, indicating refinement. Additionally, with longer
hydration times, there was no significant difference in the capillary porosity of pastes made
with 15, 20, or 25% MK, indicating that 15% replacement may be sufficient [20].
Similar kind of a study done earlier by Khatib and Wild (1996), found MK incorporation
led to pore structure refinement, with the proportion of pores having radii smaller than 20 nm
increasing significantly as the replacement level increased (Figure 3). At 14 days, pastes with
15% MK had nearly 60% of their total pore volume in sub-20 nm pores, while the control
paste had only about 30%. This represents the age at which the percentage of fine pores is the
highest and also where strength enhancement by MK reaches a maximum, confirming that the
major part of the pore refinement process occurs at a very early age. The authors attributed
this to an inhibiting layer of reaction product around the MK particles, thus terminating their
reaction with CH and preventing further pore refinement beyond 14 days. It is however noted
that MK does not have much influence on total intruded pore volume, which increased
slightly relative to controls in these evaluations. The authors suspect that this may be the
result of a phase transformation of MK/CH reaction products leading to a decrease in solid
volume and an increase in porosity [27].

Figure 3 Pore size distribution (radii < 20 nm) versus curing time for pastes containing 0-15% MK
Khatib and Wild (1996)[27].
In contrary to above, Poon et al. (2001) in its investigation of porosity and pore size
distribution of MK pastes found lower porosity and smaller average pore diameters than
control and silica fume pastes at all ages tested (3, 7, 28, and 90 days). The results indicate
that MK is more effective than silica fume in the refinement of pore structure [43]. This
contrast in the results from both Frías and Cabrera (2000) and Khatib and Wild (1996) (who
both found MK pastes to have 16% greater porosity than controls at 28 days), may be
attributed to the difference in w/cm ratios, wherein the previous studies were conducted at a
w/cm of 0.55, and the Poon et al.(2001) study was conducted with pastes prepared at a w/cm
of 0.30 [20][27][43].

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 K.Z. Farhan and W.A. Gul

Ambroise et al. (1994) found similar results to that of Poon et al.(2001) wherein a 20%
MK paste with a w/cm of 0.34 had nearly the same porosity as a control paste with a w/cm of
0.25. This implies that the porosity of an MK paste at a w/cm of 0.25 would be lower than the
control, and supports the conclusion that MK makes a significant contribution to pore
structure refinement[2]. Similar findings were further endorsed by Kostuch et al, who found
significant reduction in average pore size at 20% MK replacement and an improved
efficiency in reducing Cl and Na ion penetration [30].
Further, in conformity with the findings of Frías and Cabrera (2000) and Khatib and Wild
(1996), Khatib and Clay (2003) found that water absorption during full immersion seems to
be related to total pore volume, which has been shown to increase with MK usage.
Conversely, water penetration into concrete by capillary action has been shown to decrease
when MK is used, suggesting a discontinuity of pores [20][27][25].

5. CHLORIDE PERMEABILITY
Chlorides may enter the concrete by three main transport mechanisms: diffusion, permeation
and sorption, all of which are depend on the pore structure continuity. Although the addition
of MK reduces the total porosity, but this is not the only effect that is seen from the RCPT
tests. Since MK uses up CH, there is a lower overall ion concentration and since the
conductivity of a fluid is proportional to the dissolved ion concentration that means MK
should lower the RCPT value independent of porosity [49] [52].
Asbridge et al. (2001) examined the influence of MK on chloride diffusion kinetics in
mortars with varied volume fractions of aggregate, and hence varied volume and contribution
of the material in the ITZ. Chloride diffusion was measured both under steady-state and non-
steady-state conditions. In both cases, samples containing MK did not vary significantly
when compared to controlled ones. Diffusivity and capillary porosity both increased
markedly in control samples, indicating that the ITZ had a higher overall porosity than the
bulk paste. Interestingly, the chloride diffusivity increased sharply at aggregate volume
fractions above 35%, whereas capillary porosity increased linearly with aggregate content.
This suggested some interconnection of higher porosity ITZ regions, which resulted in
percolation and facilitates chloride transport[5].
In another study of long term investigation of chloride penetration resistance of concrete
containing high-reactivity MK (HRM), Boddy et al. (2001) casted Six concrete mixtures
with different HRM replacement at water-to-cementitious materials ratios (w/cm) of 0.30 or
0.40. The results from all of the early-age experimental work showed that higher MK content
and lower w/cm decreased diffusion, permeability, and conductivity and increased resistivity.
Resistance to chloride migration increased with increasing MK content and decreasing w/cm.
The long-term bulk diffusion testing showed a continued improvement in chloride resistance
for all of the mixtures[11]. Similarly, Batis et al. (2004) evaluate corrosion
resistance in the presence of a 3.5% NaCl solution. concluded that MK made
a positive anti-corrosive impact. Replacement with either 20% MK for sand
or 10% MK for cement improved corrosion behavior most significantly, while
higher replacement levels made no contribution[10].
Bai et al. (2003) reported that significant reductions in chloride
penetration depths were observed when PC was partially replaced with MK in
concrete, exposed to sea water. These reductions increased with both
increasing total replacement level and increasing exposure time. This was
attributed to the relative changes in intrinsic diffusivity and chloride

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 Impact of Metakaolin on Cement Mortar and Concrete: A Review

binding capacity with age exhibited by the different binder

compositions[9].
Similar results were established by Gruber et al (2001) who conducted a study to assess
the long-term performance of concrete containing HRM. Reductions in diffusion coefficients
compared to control specimens were of the order of 50% and 60% for concrete with 8% and
12% HRM, respectively. Also, the performance of the concrete containing 8% or 12% cement
replacement with HRM showed improved performance versus merely reducing the w/c from
0.4 to 0.3. Author suggested that such reductions can have a substantial impact on the service
life of reinforced concrete in chloride environments[22].

6. SULFATE RESISTANCE
Another aspect of durability that MK replacement affects is resistance to sulfate attack.
Sulfate attack is a complex process that may involve cracking and expansion of concrete as a
whole, as well as softening and disintegration of the cement paste [36]. The sulfate attack
chemical interaction is a complicated process and depends in many parameters including
concentration of sulfate ions, ambient temperature, cement type and composition, water to
cement ratio, porosity and permeability of concrete and presence of SCMs [53].
Based on its ability to refine the pore structure and improve the strength of concrete, MK
seem to be appropriate for promoting sulfate resistance. However, MK is chemically different
from many other SCMs as it has a very high alumina content. The reaction products that MK
and CH form are not only C-S-H, but also include C4AH13, C3AH6, and C2ASH8. A clear
correlation has been drawn between the tricalcium aluminate (C3A) content of a portland
cement and its susceptibility to sulfate attack [31]. If sulfate is present, ettringite is formed
from reaction of ingressing sulfates, C3A, and monosul foal uminate. The formation of
ettringite during sulfate attack can, but does not always, produce significant volume
expansion and can be detrimental to concrete life [36]. In addition, sulfate ions will react with
CH to form gypsum, which then can lead to a decrease in pore solution pH, destabilization of
hydration products, and decalcification of the C-S-H. The net effect of this form of chemical
attack is loss of adhesion and strength.
Khatib and Wild (1998) examined a commercial MK and portland cements with either an
intermediate or a high C3A content. Expansion due to sulfate attack was found to decrease
systematically with increasing MK content for both cement types. Mortars containing high
C3A cement and 0-10% MK showed rapid expansion and deterioration between 40 and 70
days of exposure to a 5% sodium sulfate solution. For the intermediate C3A content mortars,
the expansion process was delayed significantly with 10% or more MK exhibited essentially
no expansion, while those containing 0% or 5% did not begin expanding until 150 days and
did not grow rapidly until approximately 350 days[28].
Courard et al. (2003) measured sulfate resistance wherein PC mortar prisms experienced
expansion after only a few days of exposure to sodium sulfate. However in contrast, prisms
incorporated with 10% MK shrank initially and then did not change length significantly in
either direction for the duration of the test (one year)[15]. Roy et al. (2001) conducted an
extensive investigation to compare Chemical resistance MK with FA and SF. Results
generally showed SF mixtures to possess the least chemical resistance and FA to have the
greatest. MK mixtures fell in between [48].
Lee et al. (2005) in his study on the magnesium sulfate resistance of mortar and paste
specimens incorporating varying percentage of MK found specimens with 5% to 15%

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 K.Z. Farhan and W.A. Gul

replacement by MK exihibted poor resistence to sulfate attack.The negative effect of MK on

the magnesium sulfate resistance was partially attributed to the formation of gypsum but not
ettringite and thaumasite. In addition, the reduction of calcium hydroxide and the increase of
secondary C–S–H in the cement matrix due to pozzolanic reaction of metakaolin provided an
opportunity to lead to the conversion of primary and secondary C–S–H gel into the M–S–H
gel. It is concluded that it is necessary to pay special attention when using metakaolin in
concrete exposed to highly concentrated magnesium sulfate solution [32].
In a more recent investigation by Al-Akhras (2006) that MK replacement of cement
increased the sulfate resistance of concrete. The sulfate resistance of MK concrete increased
with increasing the MK replacement level. The sulfate resistance of MK concrete at w/b ratio
of 0.5 was found higher than that at w/b ratio of 0.6. Autoclaved MK concrete specimens
showed superior sulfate resistance compared to moist cured ones. The pore volume of
autoclaved MK concrete was found less than that of moist cured MK concrete. The air
entrained MK concrete showed higher improvement in the sulfate resistance than the non-air
entrained MK concrete. However, the air entrained plain concrete showed lower
improvement in the sulfate resistance than the non-air entrained concrete [1].

7. SHRINKAGE
The effect of MK on shrinkage properties is more or less contentious and not well
understood, however its been predominantly believed that due to the refinement of the pore
structure, the inclusion of MK, leads to increase in strength, decreases in permeability and
causes greater shrinkage[43]. Brooks et al. (Brooks, 2000) found that an increase
in MK content in PC-MK concrete mix, decrease the critical very early age
autogenous shrinkage, and increase the long term (200 days) autogenous
shrinkage of concrete. Concrete made using 15% MK replacement for cement
showed a 65% reduction in autogenous shrinkage as compared to controls at
24 h of age. After the age of 24 h, it was observed that all MK samples
experienced greater shrinkage than control samples. During the first two
weeks, samples containing higher MK contents shrank more; however, from
approximately five weeks on, mixtures containing less MK showed more
shrinkage. The author further calculated the total shrinkage by combining
the 24 h autogenous shrinkage with drying shrinkage of the same specimens,
to mimic field conditions. Results reveal that the overall effect of the MK
was to reduce total shrinkage of specimens. All MK mixtures showed less
total shrinkage than controls, with higher replacement levels having a more
pronounced shrinkage-reducing effect [13].
Similar results were reported by Brooks and Johari (2001) in its investigation studied the
effect of MK on the creep and shrinkage of concrete mixes containing 0%, 5%, 10% and 15%
MK. The outcomes showed that autogenous shrinkage measured from the time of initial set at
the early age of the concrete was decreased with the inclusion of MK, but the long term
autogenous shrinkage measured for the age of 24 hrs was increased at 5% replacement level.
The total shrinkage (autogenous + drying shrinkage) measured from 24 hrs was reduced by
the use of MK, while drying shrinkage was significantly less for the MK concrete than for the
control concrete. At higher MK replacement levels, the total creep, basic creep as well as
drying creep was significantly reduced. On overall, compared with the control concrete, the
greater part of the total shrinkage of the MK concrete is constituted by autogenous shrinkage,
the smaller part being drying shrinkage [12].

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 Impact of Metakaolin on Cement Mortar and Concrete: A Review

Wild et al. (1998) studied autogenous and chemical shrinkage of cement pastes with MK
contents ranging from 5 to 25%. Both autogenous and chemical shrinkage were found to
increase over control pastes, reaching a maximum between 10% and 15% replacement,
indicating an optimum in the combined effect of cement hydration and the removal of water
from the system due to reaction of the MK at this composition. At higher MK contents, both
autogenous and chemical shrinkage were found to decrease sharply. Author attributed this to
the formation of increased amounts of lower density C2ASH8 and reduced amounts of higher
density C4AH13 compounds in the presence of greater MK contents, producing an overall
volume increase and thus reducing autogenous shrinkage [57]. Similar conclusions were
made by Kinuthia et al. (2000), who found autogenous shrinkage to increase for 5 and 10%
MK but decrease for 15 and 20% replacement, although this effect could also be related to a
reduction in PC content[29].
In terms of free shrinkage alone, Caldarone et al. (1994) found that replacement with 10%
MK served to reduce shrinkage of concrete by nearly one third after 156 days of drying at
50% relative humidity. This phenomenon could be attributed, in part, to the fact that the
reaction of MK consumed more free water in the system, leaving less evaporable water
during shrinkage. This supports the conclusion that MK concretes have a lower porosity and
finer pore structure, which encourages loss of water by self-desiccation rather than by
diffusion to the surrounding environment [14]. Similar results were reported by Ding and Li
(2002) wherein MK concretes showed a faster development of shrinkage during the first
week of drying and a slower rate after that[18].
However, Rols et al(1999) measuring autogenous shrinkage in concrete up to 24h for
cementitious systems containing approximately 9% MK reported that at all times the
autogenous shrinkage was found to be lower than that in the control specimens[47]. Similarly
Gleize et al. (2007) carried out his studies on effect of MK on autogenous shrinkage of
cement pastes. It was concluded that long term autogenous shrinkage of cement MK paste
(20% replacement) with w/b ratios of 0.3 and 0.5 decreases as the cement replacement level
by MK is increased. No overall expansion of pastes was observed at early ages. The apparent
contradiction between the results of this study and other found in literature might be partly
examined by the differences in cement and MK compositions [23].

8. MECHANICAL PROPERTIES
As far as the compressive strength is concerned, partial replacement with MK helps in
reducing CH content, which in turn reduces the ITZ and consequently the overall porosity of
concrete.
Caldarone et al. (1994) in its research produced concretes with 5% and 10% MK
concrete, with w/cm of 0.40, which showed enhanced strengths at ages up to 365 days. These
specimens showed strengths an average of 10% greater than concrete incorporated with the
same amount of SF. Control specimens had the lowest strengths at all ages [14].
Similarly Wild et al. (1996), who tested concretes ranging from 1 to 90 days in age, at a
w/cm of 0.45 found that 20% replacement with MK was optimal for achieving maximum
long-term strength enhancement [56]. Similar results were established by Badogiannis et al.
(2005) studied the compressive strength of cement containing five MKs up to 180 days..
Results reveal that MK inclusion had a very positive effect on the cement strength after 2
days and specifically at 28 and 180 days. However 10% MK content seemed to be, generally,
more favorable than 20%[6].
Curcio et al. (1998) examined compressive strength development in mortars containing
15% MK. Specimens cast with three of the four MK materials tested showed higher rates of
strength evolution than controls at ages up to 28 days. However samples cast with SF and the

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 K.Z. Farhan and W.A. Gul

fourth MK (M4), which was coarser but of approximately the same chemical composition,
did not accelerate strength gain. Beyond 28 days, differences between controls and specimens
containing admixtures were smaller[16].
Ding and Li (2002), who examined 5, 10, and 15% replacement with either MK or silica
fume, found that both were effective in increasing strength beyond 14 days. At all ages, MK
and silica fume performed similarly, increasing concrete strength to almost the same extent
over controls. MK increased strength nearly linearly during the first 28 days of curing and
then slowed down -- 65-day strength was only 6-8% greater than 28-day strength[18]. Li and
Ding (2003) further investigated 10% replacement with MK, combining it with PC alone or
with both PC and ultra-fine slag. The compressive strength of the mortar mixture containing
only MK was always greater than the control mixture, and was approximately 8 MPa greater
by 28 days. Further, although initially lower, the MK-slag mixtures showed the highest 28-
day strength[33].
Vu et al. (2001) in his research to determine the degree to which kaolin could replace PC
in local mortar and concrete production, found that the optimum PC replacement level
increased with mortar maturity for all water-to-cement ratios. For early age mortars (up to
seven days), 10% replacement with MK was optimal, while 15-20% was best in the 7-28 day
range and 20-25% replacement resulted in the highest strength mortars 28 days and older. As
per the author, this implied that the pozzolanic reaction of MK may not make its peak
contribution to strength until later in the hydration process. Vu also examined the effects of
varying water content, and found that less MK was necessary to achieve maximum strength
increases at lower w/cms. For mortars with a w/cm of 0.32, 10% replacement was optimum;
for w/cm=0.44, 20% was optimum[54].
Illustrating the effect of particle size on reaction rate, Khatib and Wild (1996) showed that
increasing the specific surface of MK from 12 to 15 m2/g reduces the age at which maximum
strength enhancement occurs in MK mortars. Because of the increased surface area, MK was
able to react more rapidly, leading to a faster rate of strength evolution. This increase in
fineness also resulted in an increase in the optimum level of replacement of cement by MK,
meaning that more of the cement could be replaced by this MK without the system suffering a
lag due to dilution. Interestingly, this change in fineness did not influence the long-term (90
day) strength[27].
Qian et al. (2001) measured both compressive and tensile strength of concretes
incorporating MK. Compressive strength was found to increase substantially with increasing
MK content. In samples with 15% replacement, compressive strength had increased 51% over
controls by three days of age confirming that MK has a pronounced effect on early
strength[45]. Courard et al. (2003) and Kinuthia et al. (2000) came to a similar conclusion,
reporting enhancement in compressive strength[15][29].
Oquian and Zongjinli (2001) studied the stress–strain relationships of concrete containing
0% to 15% of MK at an incremental rate of 5%. They concluded that incorporation of MK up
to 15% has increased the tensile and compressive strength and also peak strain is increased at
increasing rate of MK up to 15%. Incorporation of MK has slightly increased the compressive
elasticity modulus[40].
In a broader consensus among authors, three elementary factors were found to influence
the strength of the concrete when it partially replaces MK. These are the filler effect, the
acceleration of PC hydration, and the pozzolanic reaction of MK with CH. According to Wild
et al.(1996) the filler effect is immediate, the acceleration of PC hydration has maximum
impact within the first 24 hours, and the pozzolanic reaction makes the greatest contribution
to strength somewhere between 7 and 14 days of age. Author also concluded that the degree

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 Impact of Metakaolin on Cement Mortar and Concrete: A Review

of positive contribution made by MK does not continue beyond 14 days, irrespective of the
replacement level, although this finding was not confirmed by other researchers [56].
Dubey and Banthia (1998) examined both MK and SF for their influence on flexural
strength of high-performance steel fiber-reinforced concrete. Both MK and silica fume
increased modulus of rupture (MOR) approximately 15% over the 100% PC sample in the
prisms not containing fibers. MK incorporation served to increase toughness contrary to the
behavior of SF[19]. In a similar study Qian et al. (2001) measured the flexural strength of
concrete beams in four point bending for varying amounts of MK replacement at both 28 and
80 days of age. For higher replacement levels, MOR increased significantly[45].
Vu et al. (2001) monitored flexural strength of MK-PC mortar prisms, and observed that
compressive and flexural strengths increased as a result of replacement with MK, even in
concentrated sulfate environments. Flexural strength showed a less pronounced increase, as
degradation due to sulfate attack first manifested itself at the specimens’ surfaces, leading to
spalling, mass loss, and thus lower MOR values[54].
With regards to modulus of elasticity (MOE), its been generally observed that MOE
increased with increase in MK content, although the rate of increase is lower than that for
compressive strength. The study performed by Qian et al. (2001) reported that at three days
curing, concrete containing 15% MK had an elastic modulus of 26.2 GPa, as compared to
24.1 GPa for the control sample at this age. At 60 days of age, 15% MK and control concretes
showed MOE values of 34.7 and 30.4 GPa, respectively[45]. Khatib and Hibbert (2004)
evaluated dynamic modulus of elasticity for w/cm=0.50 and found that MK increased MOE
at all curing times, and that 10% and 20% replacement increased MOE to the same extent
over controls[26].
Caldarone et al. (1994) reported increases in MOE associated with MK usage, as well. At
28 days, concrete containing 5% MK had increased MOE 15% over controls, while concrete
containing 5% SF increased MOE by 13%[14].

9. CONCLUSION
The Literature review puts forth compelling reasons to extend the practice of partially
replacing cement in concrete and mortar with a pozzolanic material like MK. A broader
consensus in the above literature review exists about the usability and importance of MK as a
performance enhancer in concrete.
MK has been shown to impart benefits in increasing both early and long term mechanical
properties of cement paste mortar and concrete. With regards to permeability, MK modifies
the pore structure of cement mortar and concrete with significant reduction in permeability
and resistance to transport of water and harmful ions. MK replacement of cement has shown
to impart effective resistance against sulfate attack and to some extend against chemical
ingression. A replacement level of 10 to 15% MK has shown very good results in this
regards. Further, Inclusion of high reactive MK as partial replacement in optimal range is
shown to control detrimental expansion due to ASR in concrete. However as a negative
aspect, MK has also been shown to increase shrinkage and heat evolved during hydration,
which can be detrimental and needs to be further researched and worked on.
Last but not the least, with the invent of new technological innovations at nano and micro
level, it is possible to tailor compositions and particle size to increase overall sustainability of
concrete in general and to meet the constraints of environment in particular.

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