Materials and Structures (2007) 40:1161–1171
DOI 10.1617/s11527-007-9258-5
ORIGINAL ARTICLE
Comparative study on strength, sorptivity, and chloride
ingress characteristics of air-cured and water-cured
concretes modified with metakaolin
Erhan Güneyisi Æ Kasım Mermerdaş
Received: 29 November 2006 / Accepted: 2 May 2007 / Published online: 25 May 2007

RILEM 2007
Abstract This paper reports an investigation in
which the performance of plain and metakaolin
(MK)-modified concretes were studied under two
different curing regimes. The purpose of this study is
to evaluate the effectiveness of MK in enhancing the
strength and permeation properties of concrete. MK
was used to replace 0–20% of Portland cement by
weight in concrete with two water-binder (w/b) ratios
of 0.35 and 0.55. The change in compressive strength,
sorptivity, and chloride ingress with age at all cement
replacement levels under both air and water curing
are compared with those of the control concrete. The
results indicated that the inclusion of MK greatly
reduced sorptivity and chloride permeability of
concrete in varying magnitudes, depending mainly
on replacement level of MK, w/b ratio, curing
condition, and chloride exposure period. It was found
that under the inadequate or poor curing, MK-
modified concretes suffered a more severe loss of
compressive strength and permeability-related dura-
bility than the plain concretes.
Keywords Chloride ingress
Concrete
Curing
regime
Metakaolin
Sorptivity
E. Güneyisi (&)
K. Mermerdaş
Department of Civil Engineering, Gaziantep University,
Gaziantep 27310, Turkey
e-mail: guneyisi@gantep.edu.tr
1 Introduction
Concrete is the most important element of the
infrastructure and well-designed concrete can be a
durable construction material. However, the environ-
mental aspects of Portland cement are a growing
concern, as cement manufacturing is responsible for
about 2.5% of total worldwide emissions from
industrial sources. One effective way to diminish
the environmental impact is to use natural pozzolans
and/or supplementary cementing materials, as a
partial cement replacement. This strategy will have
the potential to reduce costs, conserve energy, and
reduced waste volumes [1]. The cementing materials
that are widely used, concrete constituents, are fly
ash, granulated blast furnace slag, and silica fume [2].
Metakaolin (MK), produced by controlled thermal
treatment of kaolin, is the most recent mineral
admixture to be commercially introduced to the
concrete construction industry. The utilization of
calcined clay in the form of high-reactivity MK as
pozzolans for concrete has received considerable
interest in recent years. This interest has been focused
on the consumption of calcium hydroxide (CH)
produced by cement hydration which is associated
with poor durability. Thus, the use of MK improves
long-term strength and durability. In addition, it is
also possible to obtain early strength enhancement
through the filling effect [3].
According to the literature, it has been claimed
that concrete incorporated with MK exhibits pre-
1162
mium-level engineering properties comparable to
silica fume concrete [4, 5]. This results from the
characteristics of its chemical composition, fineness,
and poorly crystalline nature [6]. The research work
about the use of MK deals with two main areas. In the
first one, the heat treatment parameters, the dehaydr-
oxylation/amorphization process of the kaolinite, and
the formation of the metakaolinite have been studied
[6–9]. The second one concerns the filling and
pozzolanic behavior of MK and its influence on
cement and concrete properties [4, 10–24]. Research
related to the effect of MK on the performance of
concrete is in progress due to the fact that MK is a
relatively new mineral admixture for concrete indus-
try. MK is also considered as an alternative supple-
mentary cementing material. It is comparable to silica
fume in pozzolanic reactivity, but is lower in price
[16].
It is generally agreed that ingress of aggressive
species into concrete leads, in many structures, to
long-term deterioration. The concrete performance
depends on mainly on the environmental conditions,
the microstructures, and the chemistry of the con-
crete. Here, the continuation of hydration reactions in
portland cement is essential to improve the potential
strength and durability of concrete. This continuation
depends on the type (chemical and mineralogical
composition) and fineness of cement, the type and the
amount of supplementary material present, the water-
binder (w/b) ratio and the curing condition, especially
at early ages [25]. It is obvious that those factors are
essential to obtain the durable concrete structures.
Curing is necessary for concrete to fully realize its
potential properties [26, 27]. The curing becomes
more important for concrete incorporating pozzolans,
especially in hot and dry environments [28].
Recent works have shown that MK is effective on
enhancing the durability performance of concrete, for
example, alkali–silica reaction [21] and resistance to
sodium sulfate attack [17]. In particular, concerning
resistance to chloride ingress of MK concrete, few
studies have been reported. Boddy et al. [19] studied
long-term testing of the chloride penetration resis-
tance of concrete containing high reactivity MK.
Concrete mixtures were cast with 0, 8, or 12% by
mass replacement of Portland cement with MK at w/b
ratios of 0.30 and 0.40. They found that resistance to
chloride migration increased with increasing MK
content and decreasing w/b. The long-term bulk
Materials and Structures (2007) 40:1161–1171
diffusion testing showed a continued improvement in
chloride resistance for all of the mixtures. In the study
of Gruber et al. [21], it was also concluded that the
use of 8% and 12% MK significantly lowered the
chloride ion diffusion coefficient of concrete. The
level of reduction compared to control specimens was
on average 50% and 60% for mixes with 8% and 12%
MK, respectively. Furthermore, Bai et al. [20]
showed that significant reductions in chloride pene-
tration depths occurred when Portland cement was
partially replaced with pulverized fuel ash and MK.
These reductions increased with both increasing total
replacement level and increasing exposure time.
According to Ding and Li [16], the incorporation of
both silica fume and MK in concrete greatly reduced
the chloride diffusion rate. It was found that 15% MK
had a significant improvement while 5% MK had also
some improvement on the chloride resistance.
In this study, MK was used as a replacement for
Portland cement and the effect of MK replacement,
ranging from 0% to 20% by weight upon material
properties was examined. For this, six different
concrete mixtures with two w/b ratios of 0.35 and
0.55 were designed. The compressive strength, sorp-
tivity, and chloride ingress characteristics of the MK-
modified concretes were determined at different ages
up to 90 days. The study also investigates the effect
of different curing regimes on the permeability-
related durability of concrete incorporating MK as a
supplementary cementing material. Based on the test
results, the effects of MK, w/b ratio, age, and curing
procedure upon concrete properties were discussed.
2 Experimental program
2.1 Materials
The materials used in this investigation were Portland
cement, MK, fine aggregate, coarse aggregate and
high range water-reducing admixture (HRWA). Port-
land cement (CEM I 42.5R) conforming to the
Turkish standard TS EN 197–1 (which mainly based
on the European EN 197–1) and commercially
available MK were utilized as cementitious materials.
MK is produced by thermal activation of high purity
kaolin clay, which originated from India, within a
specific temperature range. The MK used in this
study is a white powder with a Hunter L whiteness
Materials and Structures (2007) 40:1161–1171 1163

value greater than 90 (on a scale from ‘‘0-black’’ to
‘‘100-maximum whiteness’’). It has a specific gravity
of about 2.60, a specific surface area of 8600 m2/kg,
and an average particle size less than 2 mm. The
chemical compositions and the physical properties of
Portland cement and MK are given in Table 1. The
fine aggregate was a mix of river sand and crushed
sand whereas the coarse aggregate was river gravel
with a maximum particle size of 16 mm. Both
aggregates were obtained from local sources. Prop-
erties of the aggregates are presented in Table 2. A
commercially available sulphonated naphthalene
formaldehyde-based high range water-reducing
admixture was used to give a consistent workability.
Its specific gravity was approximately 1.22.
2.2 Details of mixtures, specimens, and curing
regimes
Two series of control mixtures with w/b ratios of 0.35
(Series 1) and 0.55 (Series 2) were designed. To
develop the MK-modified concrete mixtures, the
Portland cement was partially replaced with 10% and
20% MK (by weight) for both series. Thus, totally six
different mixtures were prepared in this study. Details
of the mixtures are given in Table 3. Grading of the
aggregate mixture was kept constant for all concretes.
The mixtures given in Table 3 were designed to have
slump values of 140 ± 20 mm and 180 ± 20 mm for
w/b ratios of 0.35 and 0.55, respectively for the ease
of handling, placing, and consolidation. The high
range water-reducing admixture was added at the
time of mixing to achieve the specified slump at each
w/b ratio. All concretes were mixed in accordance
with ASTM C192 standard in a power-driven
revolving pan mixer. For each mixture, twelve
100 · 100 · 100 mm cube and eight
100 · 100 · 500 mm prism specimens were cast
and compacted by a vibrating table. After casting, the
moulded specimens were covered with a plastic sheet
and left in the casting room for 24 h. They were then
demoulded and divided into two equal groups and
cured under the given conditions below. Thereafter,
they were tested in accordance with the specified test
methods.
2.3 Air curing (AC)

Table 1 Chemical compositions and physical properties of Specimens were left to cure continuously in the
cementitious materials used
laboratory under ambient condition until the test age.
Item Portland Metakaolin The temperature was moderately controlled at 20oC,
cement
but humidity was uncontrolled and generally ranged
SiO2 (%) 19.73 51.8 between 50% and 80%. Specimens were designated as
Al2O3 (%) 5.09 45.8 AC and are called air-cured at ambient temperature.
Fe2O3 (%) 3.99 0.35
CaO (%) 62.86 0.01 2.4 Water curing (WC)
MgO (%) 1.61 0.03
SO3 (%) 2.62 – Specimens were left to cure continuously in water at
Na2O (%) 0.18 0.13 20 ± 2oC until the test age. Specimens were
K2O (%) 0.80 0.06 designated as WC and are called water-cured at
Cl (%) 0.01 – controlled temperature.
Insoluble residue (%) 0.24 –
Loss on ignition (%) 1.90 0.91 2.5 Test methods
Free lime (%) 0.57 –
Specific gravity (g/cm3) 3.14 2.60 2.5.1 Compressive strength
Setting time, Vicat needle Initial/ 2-46/3-44 –
Final (h-min) The concrete cubes (100 · 100 · 100 mm) were used
Expansion, Le Chatelier apparatus 1 – for the compressive strength test at 28 and 90 days.
(mm)
The compression test was carried out on the speci-
Specific surface area (m2/kg) 327 8600
mens by a 3000 kN capacity testing machine. The test
Color Gray White
procedure followed during the test was in conformity
1164 Materials and Structures (2007) 40:1161–1171

Table 2 Sieve analysis and

Sieve size (mm) Fine aggregate Coarse aggregate
physical properties of
aggregates River sand Crushed sand No I No II

16.0 100 100 100 100

8.0 100 100 31.5 1.9
4.0 86.6 95.4 1.0 1.1
2.0 56.7 63.3 0.5 1.0
1.0 37.7 39.1 0.5 0.9
0.50 25.7 28.4 0.5 0.9
0.25 6.7 16.4 0.4 0.8
Fineness modulus 2.87 2.57 5.66 5.93
Specific gravity 2.66 2.45 2.72 2.73
Absorption, % 0.55 0.92 0.45 0.42

Table 3 Mixture proportions of the concrete

Concrete w/b MK Cement MK (kg/ Water Fine aggregate Coarse aggregate HRWAa
series ratio (%) (kg/m3) m3) (kg/m3) (kg/m3)
River sand Crushed sand No I (kg/ No II (kg/
(kg/m3) (kg/m3) m3) m3)

1 0.35 0 450 0 158 724 233 611 241 7.9

0.35 10 405 45 158 720 232 608 240 10.1
0.35 20 360 90 158 717 231 605 239 12.4
2 0.55 0 350 0 193 726 234 612 242 3.5
0.55 10 315 35 193 723 233 610 241 4.4
0.55 20 280 70 193 721 232 608 240 6.1
a
HRWA: High-range water-reducing admixture

with ASTM C39. Three specimens from each mixture
were tested at each testing age.
2.5.2 Sorptivity
The sorptivity test measures the rate at which water is
drawn into the pores of concrete. For this, three test
specimens having a dimension of
100 · 100 · 100 mm cut from 100 · 100 · 500 prism
specimens were employed. The specimens were dried
in an oven at about 50 ± 5oC until constant mass and
then allowed to cool to the ambient temperature in a
sealed container. Afterwards, the sides of the spec-
imens were coated by paraffin wax and as shown in
Fig. 1, the sorptivity test was carried out by placing
the specimens on glass rods in a tray such that their
bottom surface up to a height of 5 mm is in contact
with water. This procedure was considered to allow
free water movement through the bottom surface. The
total surface area of water within the tray should not
be less than 10 times that of the specimen cross-
sectional area [29]. The specimens were removed
from the tray and weighed at different time intervals
up to 1 h to evaluate mass gain. The volume of water
absorbed was calculated by dividing the mass gained
by the nominal surface area of the specimen and by
the density of water. These values were plotted
concrete sample
paraffin wax
water
Fig. 1 Measurement of concrete sorptivity
Materials and Structures (2007) 40:1161–1171
against the square root of time. The slope of the line
of the best fit was defined as the sorptivity coefficient
of concrete. For each test, measurements were
obtained from three specimens and the average
values were reported.
2.5.3 Chloride ion penetration
The prismatic test specimens (100 · 100 · 500 mm)
after being subjected to 28 days of initial curing
procedures were soaked continuously in 4% NaCl
solution for 90 days. After the 90-day chloride
exposure period, the test specimens were withdrawn
from the soaking tank at 7, 14, 28, 56, and finally
90 days to determine the depth of chloride penetration
into plain and MK-modified concretes. For this
purpose, the prisms were first split at mid point and
the freshly split surfaces were soon sprayed with 0.1 N
silver nitrate (AgNO3) solution. The AgNO3 solution
preferentially reacts with the free chloride present in
the harden matrix to form a white precipitate of silver
chloride (AgCl); whereas at greater depths, where free
chlorides are absent, AgNO3 reacts with the hydrox-
ides to form a brown precipitate of silver oxide (AgO).
Thus, the depth of chloride penetration is clearly
indicated as the boundary of color change. View of the
boundary of color change after spraying AgNO3
solution for the plain and MK-modified concrete
specimens is illustrated in Fig. 2. The white coloring
(formation of silver chloride) occurs wherever the
concentration of free chloride ion is greater than
0.15% by weight of cement. Measuring the depth of
color change was performed from the four sides of the
split section at intervals of 20 mm. Measurements
Fig. 2 Photographs
showing the typical
boundary of color change
on the specimens after the
28 day chloride exposure
period (a) plain concrete
(MK0) and (b) MK
concrete (MK20)
1165
made close to the corners of the section and ahead of
the coarse aggregates were ignored. The test method
followed in the present investigation to determine the
depth of chloride penetration is reliable and accurate,
and has also been recommended by other researchers
[30–33].
3 Test results and discussion
3.1 Compressive strength
The data concerning the variation of compressive
strength with w/b ratio, concrete age, and curing
condition for concretes incorporated with 0, 10, and
20% MK are plotted in Fig. 3. The strength values for
the plain and MK-modified concretes ranged from
36.1 to 72.0 MPa and from 37.4 to 93.6 MPa,
respectively. The effect of MK on compressive
strength of concrete is well observed in Fig. 3. The
figure indicated that there was a systematic increase in
compressive strength with the increase in MK content.
This is more pronounced for concretes subjected to
water curing (WC). The degree of strength enhance-
ment (due to MK) is in direct relation to the
parameters of age, curing condition, and the amount
of MK present. MK not only increases the early
(28 days) strength of concrete but also increases the
later strength (90 days). For example, the increase in
compressive strength with increasing age was ob-
served to increase up to approximately 11% and 20%
for the plain and MK-modified concretes, respec-
tively. It was also noted that for both w/b ratios,
concretes with MK had remarkably higher compres-
1166 Materials and Structures (2007) 40:1161–1171

1.20
100 28 days
Compressive strength (MPa)

90 days

Normalized compressive strength, fc,air/fc,water

90
80
70 1.00
60
50
40
0.80
30
20
10
0 0.60
MK0

MK10

MK20

MK0

MK10

MK20

MK0

MK10

MK20

MK0

MK10

MK20
water curing air curing water curing air curing
0.40
w/b=0.35 w/b=0.55 28 day air-cured MK concrete
Concrete type 90 day air-cured MK concrete
0.20 28 day air-cured plain concrete
Fig. 3 Variation in compressive strength of plain and MK- 90 day air-cured plain concrete
modified concretes subjected to different curing regimes Water curing
0.00
0 20 40 60 80 100 120
Compressive strength of concrete subjected to water
sive strength than the plain ones. The percent increase curing (MPa)
in the strength with the use of MK ranged from
approximately 10–30% for the water-cured concretes Fig. 4 Influence of curing condition on 28 and 90 day
compressive strengths of concretes incorporated with MK
but from 2% to 14% for the air-cured concretes,
depending mainly on the variation in w/b ratio, age,
and replacement level of MK. The addition of MK 3.2 Sorptivity
into the matrix improves the bond between the cement
paste and aggregate particles as well as increasing the The change in sorptivity with w/b ratio, concrete age,
density of the cement paste which in turn significantly and curing condition for the plain and MK-modified
improves the compressive strength of the concretes. concretes are given in Fig. 5. It is apparent that
According to the literature, the main factors that affect sorptivity decreases systematically with an increase
the contribution of MK in strength are (a) the filling in curing period (from 28 to 90 days), and the
effect, (b) the dilution effect, and (c) the pozzolanic gradients of the sorptivity tends to decrease with
reaction of MK with CH [12]. increase in the replacement level of MK. At early age
The effect of curing condition on the 28- and 90- (28 days), the sorptivity values are clearly reflected in
day compressive strength of the plain and MK- the strength values. Thus, the concretes with the
modified concretes is illustrated in Fig. 4. For both lowest sorptivities have the highest strengths, espe-
concrete types, air curing (AC) resulted in signifi- cially for those subjected to water curing regime.
cantly lower 28- and 90-day strengths as compared to Increasing the MK content reduced both the 28- and
water curing (WC). It was observed that the ratios for 90 day sorptivities of the concrete. This is particularly
the plain and MK-modified concretes subjected to AC for the high w/b ratio water-cured concretes. The
did not fall within 10% of equality and deviated up to
approximately 24% and 34% from those cured
under WC, respectively. This implies that the reduc- 0.18 28 days
0.16 90 days
tion in strength is particularly large for concretes with
Sorptivity (mm/min )
0.5

0.14
MK, especially at later age (90 days). For inadequate 0.12
0.10
curing (air curing, AC), the absence of moist curing 0.08
0.06
resulted in lower strengths where the concrete 0.04
containing MK suffered more at both testing ages 0.02
0.00
(28 and 90 days). This can be attributed to the lack of
MK0

MK10

MK20

MK0

MK10

MK20

MK0

MK10

MK20

MK0

MK10

MK20

development of hydration and pozzolanic reactions to water curing air curing water curing air curing
produce a dense microstructure as well as the w/b=0.35 w/b=0.55
extensive shrinkage cracking, which may have Concrete type

developed due to continuous air curing which has Fig. 5 Variation in sorptivity of plain and MK-modified
also been indicated by other researchers [28, 34]. concretes to different curing regimes
Materials and Structures (2007) 40:1161–1171 1167

sortivity values of the concrete containing MK were This implies that MK concretes are very sensitive to
approximately from 2% to 36% and from 8% to 60% curing method adopted. Figure 6 also revealed that
lower than that of the plain concretes at 28 and there is a marked difference in sorptivity values for
90 days, respectively, depending on w/b ratio, the plain and MK-modified concretes at 90 days as a
amount of MK used, and curing regime. Generally, result of pozzolanic reaction which effectively
MK concrete performed better than the control reduces the volume of pore space.
concrete and marked improvements in terms of lower
rate of water penetration through capillary suction 3.3 Resistance to chloride ion penetration
were apparent, particularly under water curing con-
dition. This reduced sorptivity reflects a finer pore Figure 7 demonstrates the chloride penetration depth
structure that would, for example, inhibit ingress of measured periodically (at 7, 14, 28, 56, and 90 days)
aggressive elements into the pore system [35]. through the plain and MK-modified concretes sub-
Taşdemir [36] have also shown that type and fineness jected to two different initial curing followed by
of mineral admixtures (such as fly ash, limestone immersion in salt solution. Depths of chloride
filler, sandstone filler, and silica fume) together with penetration for plain concretes subjected to the initial
curing condition affect greatly the pore structure of curing conditions of AC and WC were in the range of
concrete and it was reported that a significant about 8–23 mm and 6–17 mm, respectively, depend-
reduction in sorptivity for the blended mixtures was ing mainly upon w/b ratio and immersion period in
obtained when the proper curing was applied.
A comparison of air-cured and water-cured con-
crete sorptivity with age for the plain and MK- 25
(a)
modified concretes is given in Fig. 6. The figure
Depth of chloride penetration (mm)

distinguishes the prevailing effect of water curing on 20

the MK specimens, especially tested at later age

(90 days). It was noted that air curing caused 15

significant increase in sorptivity of both plain and

especially MK concretes as compared to water 10
MK0-WC
curing. Results showed that ratios for plain and MK MK10-WC

concrete specimens under air curing condition lied 5 MK20-WC

MK0-AC
within a range of 1.2–1.4 and 1.4–2.5, respectively. MK10-AC
MK20-AC
0
0 2 4 6 8 10 12 14
3.00 Immersion period (weeks)
28 day air-cured MK concrete
90 day air-cured MK concrete 25
2.50 28 day air-cured plain concrete (b)
Depth of chloride penetration (mm)
Normalized sorptivity, Sair/Swater

90 day air-cured plain concrete

Water curing 20
2.00

15
1.50

10
1.00 MK0-WC
MK10-WC
MK20-WC
5
MK0-AC
0.50 MK10-AC
MK20-AC
0
0.00 0 2 4 6 8 10 12 14
0 0.05 0.1 0.15 0.2 Immersion period (weeks)
Sorptivity of concrete subjected to water curing
(mm/min0.5) Fig. 7 Variation in chloride penetration depth with immersion
period for plain and MK-modified concretes subjected to
Fig. 6 Influence of curing condition on 28 and 90 day different curing regimes (a) w/b ratio: 0.35 and (b) w/b ratio:
sorptivity coefficients of concretes incorporated with MK 0.55
1168
salt solution. However, the concretes incorporating
MK had comparatively lower chloride penetration
depths which ranged from 6 to 20 mm for the initial
curing of AC and from 2 to 15 mm for the initial
curing of WC. It was also observed that the chloride
penetration depths of all concretes decreased with
decreasing w/b ratio from 0.55 to 0.35, irrespective of
initial curing conditions. The effect of w/b ratio was
well observed at the end the 7-day chloride exposure
period for all initial curing conditions. The plain
concretes with high w/b ratio gave about 2.0 and 1.8
times greater chloride penetration depths than those
with low w/b ratio for the initial curing conditions of
AC and WC, respectively. However, these values for
the MK-modified concretes ranged from 1.7 to 2.3,
depending on replacement level of MK and initial
curing period. The order of the increase reduced with
the increasing chloride immersion period (from 7 to
90 days) for both concretes. In addition, the test
results exhibited that MK-modified concretes had
noticeably lower chloride penetration depth in com-
parison to the plain concretes during the 90-day
chloride exposure period, particularly under the
initial water curing condition. For example, at the
end of the 90-day immersion period, the depth of
chloride penetration for high and low w/b ratio water-
cured concretes containing 10% MK were approxi-
mately 7% and 10% lower than that of the control
concrete at similar condition, respectively. However,
those for concretes with 20% MK were about 17%
and 21%. This result agrees well with the results from
a previous study by Ding and Li [16]. They demon-
strated that the incorporation of MK in concrete
reduced the chloride diffusion rate significantly. It
was concluded that 5% MK had some improvement
on the chloride diffusivity while 15% MK has a
significant improvement.
The chloride penetration depths measured for both
plain and MK-modified concrete specimens during
the 90-day chloride exposure period were then used
to compute the chloride penetration coefficient, K
(mm per square root of week). The magnitudes of K
were estimated by using the empirical relationship
(3.1) between the depth of chloride penetration (X)
and duration of immersion in salt solution (t) as
proposed by Bakker [37].
pffi
X ¼ aþK t ð3:1Þ
Materials and Structures (2007) 40:1161–1171
The chloride penetration coefficient, K, is used in
the present investigation as an indicator of the
resistance of concrete against chloride penetration.
Several authors previously used the similar test
method to calculate this parameter for comparing
the resistance to chloride ion penetration of different
mortars and concretes [30, 32].
Figure 8 shows the chloride penetration coeffi-
cients (K) of all concretes. The figure indicated that
for the plain and MK-modified concrete specimens
pre-cured for a similar condition, an increase in w/b
ratio leads to a larger K or faster rate of chloride
penetration. Moreover, as expected, for the concretes
of all w/b ratios, K marginally decreased with
improving pre-curing condition. For a given pre-
curing condition and w/b ratio of the mix, the
magnitudes of K for the plain concrete specimens
were also relatively higher compared to the corre-
sponding K for the MK-modified concrete specimens.
It was also noted that increasing the replacement
level of MK decreased considerably the chloride
diffusivity. Moreover, graphs in Fig. 8 showed that
the concretes made with 20% MK had the lowest
chloride penetration coefficient, irrespective of w/b
ratio and pre-curing condition.
The effect of initial curing condition on the
chloride penetration coefficient of the plain and
MK-modified concretes is illustrated in Fig. 9. Lack
of proper curing produced similar effect on the
chloride ingress to that on the sorptivity of concrete.
Air curing leads to higher chloride penetration
coefficient for both plain and especially MK con-
cretes. It was observed that the ratio of the chloride
8.00
WC
7.44
7.04
Chloride penetration coefficient, K
7.00 AC
6.43
6.00 5.71
(mm per sqr t week)
5.42
4.90 4.85
5.00
4.17
4.52
4.16
4.00 3.71
3.14
3.00
2.00
1.00
0.00
MK0 MK10 MK20 MK0 MK10 MK20
w/b=0.35 w/b=0.55
Concrete type
Fig. 8 Variation in chloride penetration coefficient of plain and
MK-modified concretes subjected to different curing regimes
Materials and Structures (2007) 40:1161–1171 1169

2.00 of the strength for the MK concretes was remarkably

Normalized chloride penetration coefficient, Kair/Kwater

Air-cured MK concrete
Air-cured plain concrete higher than that for the plain concretes, especially
Water curing
under water curing. In the case of the permeability
1.50
related-durability tests, the range of sorptivity coeffi-
cients for the MK concretes was comparatively lower
1.00
than that for the plain cement concretes. The ratio of
sorptivity coefficient of the plain concretes to that of
MK concretes ranged from 1.01 to 2.03, depending
0.50 mainly on the curing regimes. The behavior observed
in the sorptivity of the concretes was quite similar to
that in depth and coefficient of chloride penetration.
0.00 The concretes containing MK had lower chloride
0 1 2 3 4 5 6 7 8
Chloride penetration coefficient of concrete subjected to water
permeability than the plain concretes. The difference
curing (mm/sqrt week) between both concrete types reached as high as 33%
with improving the initial curing regime.
Fig. 9 Influence of curing condition on chloride penetration
coefficient of concretes incorporated with MK

4 Conclusions
penetration coefficient of the specimens pre-cured
under air curing to those pre-cured under water curing From the results presented in this paper, the following
for the plain concrete deviated up to 30%. However, conclusions can be drawn:
this ratio for concretes containing MK lied within a
range of 32–52%. This indicates that the chloride 1. This study indicated that the inclusion of MK
penetration of the concretes containing MK is more into concrete significantly enhanced the strength
sensitive to the lack of curing. This is due to the and especially permeability-related durability
change in hydration kinetics of total cementitious characteristics of the concrete in varying magni-
material and the hydration development at the curing tudes. Concrete containing MK shows higher
cessation time [38]. strength than that of the plain concrete but
Table 4 summarized the comparison of the order of marginally lower chloride penetration depths and
the variation in the concrete properties (compressive sorptivities. The order of the magnitude is
strength, sorptivity, depth of chloride penetration at depended mainly on replacement level of MK,
90 days, and chloride penetration coefficient). As it is w/b ratio, concrete age, and curing condition.
seen from the table, the four measured concrete 2. Curing played a critical role in realizing the full
properties had similar tendency for both plain and potential of concrete. It is necessary to pay
MK-modified concretes in that the latter had better careful attention when using MK in concrete due
performance in comparison to the former. The range to the fact that the performance properties of the

Table 4 Comparison of the

Concrete property Curing Plain MK-modified Ratio (plain/
order of the variation in the
condition concretes concretes metakalolin
concrete properties with
concretes)
respect to curing conditions
and concrete types Range of compressive strength AC 36.1–60.1 37.4–62.2 0.96–0.97
(MPa) WC 45.3–72.0 50.0–93.6 0.76–0.90
Range of sorptivity coefficients AC 0.100–0.171 0.071–0.169 1.01–1.41
(mm/min0.5) WC 0.071–0.129 0.035–0.084 1.54–2.03
Range of chloride penetration AC 17.4–22.2 14.7–20.4 1.09–1.18
depths at 90 days (mm) WC 12.9–17.1 10.8–15.4 1.11–1.19
Range of chloride permeability AC 5.42–7.44 4.52–7.04 1.05–1.20
coefficients(mm/week0.5) WC 4.17–5.71 3.14–4.85 1.18–1.33
1170
MK-modified concretes are more sensitive to
curing method adopted.
3. Irrespective of w/b ratio and replacement levels
of MK, air-cured concretes exhibit lower strength
and considerably higher permeability relative to
equivalent concrete that is water cured. It was
observed that the strength of the plain and MK-
modified concretes subjected to air curing devi-
ated up to 24% and 34% from those cured
under water, respectively. The application of air
curing also resulted in marked differences with
respect to the water curing in terms of sorptivity
and chloride ingress characteristics of the con-
cretes, particularly for those made with MK.
4. The comparison of the order of the variation in
the concrete properties (strength, sorptivity coef-
ficient, depth of chloride penetration at 90 days,
and chloride penetration coefficient) pointed out
that there is a strong correlation between them.
The four measured concrete properties had
similar tendency for both plain and MK-modified
concretes in that the latter had better performance
in comparison to the former.
In this study, a colourimetric method of measuring
the depth of chloride penetration into concrete by
spraying a 0.1N AgNO3 solution was employed to
compare the chloride penetration resistance of the
plain and MK-modified concretes. However, as a
further research, the use of some additional long term
tests such as divided diffusion cell or ponding test
would be helpful to measure or predict the chloride
content of such concretes for comparison purposes.
Acknowledgements The authors would like to thank to Mr.
Vakıf Kiriş for his invaluable assistance during the laboratory
phase of the study.
References
1. Aldea CM, Young F, Wang K, Shah SP (2000) Effects of
curing conditions on properties of concrete using slag
replacement. Cem Concr Res 30:465–472
2. Neville AM (1996) Properties of concrete. Addison Wes-
ley Logman, 4th and final edn, England
3. Cook DJ (1986) Calcined clay, shale, and other soils. In:
Swamy RN (ed) Cement replacement materials, Surrey
University Press, pp. 40–72
4. Dunster AM, Parsonage JR, Thomas MJK (1993) Pozzo-
lanic reaction of metakaolinite and its effects on Portland
cement hydration. J Mater Sci 28:1345–1351
Materials and Structures (2007) 40:1161–1171
5. Kristof E, Juhasz AZ, Vassanyi I (1993) The effect of
mechanical treatment on the crystal structure and thermal
behavior of kaolinite. Clays Clay Miner 41:608–612
6. Frias M, Cabrera J (2001) Influence of MK on the reaction
kinetics in MK/lime and MK-blended cement systems at
20oC. Cem Concr Res 31:519–527
7. Gamiz E, Melgosa M, Maranon MS, Garcia JMM, Delgado
R (2005) Relationships between chemico–mineralogical
composition and color properties in selected natural and
calcined Spanish kaolins. Appl Clay Sci 28:269–282
8. Shvarzman A, Kovler K, Grader GS, Shter GE (2003) The
effect of dehyroxylation/amorphization degree on pozzo-
lanic activity of kaolinite. Cem Concr Res 31:405–416
9. Kakali G, Perraki T, Tsivilis S, Badogiannis E (2001)
Thermal treatment of kaolin: the effect of mineralogy on
the pozzolanic activity. Appl Clay Sci 20:73–80
10. Caldarone MA, Gruber KA, Burg RG (1994) High-reac-
tivity metakaolin: a new generation mineral admixture.
Concr Int 16(11):37–40
11. Zhang MH, Malhotra VM (1995) Characteristics of a
thermally activated alumino-silicate pozzolanic material
ant its use in concrete. Cem Concr Res 25:1713–1725
12. Wild S, Khatip JM, Jones A (1996) Relative strength,
pozzolanic activity and cement hydration in superplasti-
cized metakaolin concrete. Cem Concr Res 26:1537–1544
13. Khatib JM, Wild S (1996) Pore size distribution of me-
takaolin paste. Cem Concr Res 26:1545–1553
14. Brooks JJ, Johari MAM (2001) Effect of metakaolin on
creep and shrinkage of concrete. Cem Concr Compos
23:495–502
15. Sabir BB, Wild S, Bai J (2001) Metakaolin and calcined
clays as pozzolans for concrete: a review. Cem Concr
Compos 23:441–454
16. Ding JT, Li Z (2002) Effects of metakaolin and silica fume
on properties of concretes. ACI Mater J 99(4):393–398
17. Khatib JM, Wild S (1998) Pore size distribution of me-
takaolin paste. Cem Concr Res 28(1):83–92
18. Bai J, Sabir BB, Wild S, Kinuthia J (2000) Strength
development in concrete incorporating PFA and metakao-
lin. Mag Concr Res 52(3):153–162
19. Boddy A, Hooton RA, Gruber KA (2001) Long-term
testing of the chloride-penetration resistance of concrete
containing high-reactivity metakaolin. Cem Concr Res
31:759–765
20. Bai J, Wild S, Sabir BB (2003) Chloride ingress and
strength loss in concrete with different MK-PFA-PC binder
compositions exposed to synthetic seawater. Cem Concr
Res 33:353–362
21. Gruber KA, Ramlochan T, Boddy A, Hooton RD, Thomas
MDA (2001) Increasing concrete durability with high-
reactivity metakaolin. Cem Concr Compos 23:479–484
22. Lee ST, Moon HY, Hooton RD, Kim JP (2005) Effect of
sodium concentration and replacement levels of metakao-
lin on the resistance of mortars exposed to magnesium
sulfate solutions. Cem Concr Res 35:1545–1553
23. Batis G, Pantazopoulou P, Tsivilis S, Badogiannis E (2005)
The effect of metakaolin on the corrosion behavior of ce-
ment mortars. Cem Concr Compos 27:458–467
24. Revilla CF, Ramirez SM, Varela MTB (2006) Modelling
of slaked lime-metakaolin mortar engineering characteris-
Materials and Structures (2007) 40:1161–1171
tics in terms of process variables. Cem Concr Compos
28:458–467
25. Neville AM, Brooks JJ (1990) Concrete technology.
Longman scientific and Technical, Singapore
26. Khatri RP, Sirivivatnanon V, Yu LK (1997) Effect of
curing on water permeability of concretes prepared with
normal Portland cement and with slag and silica fume.
Mag Concr Res 49(180):162–172
27. Güneyisi E, Özturan T, Gesoğlu M (2005) A study on
reinforcement corrosion and related properties of plain and
blended cement concretes under different curing condi-
tions. Cem Concr Compos 27(4):449–461
28. Ramezanianpour AA, Malhotra VM (1995) Effect of cur-
ing on the compressive strength, resistance to chloride ion
penetration and porosity of concretes incorporating slag,
fly ash, or silica fume. Cem Concr Compos 17:125–133
29. Razak HA, Chai HK, Wong HS (2004) Near surface
characteristics of concrete containing supplementary
cementing materials. Cem Concr Compos 26:883–889
30. Wee TH, Suryavanshi AK, Tin SS (2000) Evaluation of
rapid chloride permeability test (RCPT) results for con-
crete containing mineral admixtures. ACI Mater J
97(2):221–232
31. Otsuki N, Nagataki S, Nakashita K (1992) Evaluation of
AgNO3 nitrate solution spray method for measurement of
1171
chloride penetration into the hardened cementitious matrix
materials. ACI Mater J 89(6):587–592
32. Wee TH, Suryavanshi AK, Tin SS (1999) Influence of
aggregate fraction in the mix on the reliability of the rapid
chloride permeability test. Cem Concr Compos 21:59–72
33. Meck E, Sirivivatnanon V (2003) Field indicator of chlo-
ride penetration depth. Cem Concr Res 33:1113–1117
34. Toutanji HA, Bayasi Z (1999) Effect of curing procedures
on properties of silica fume concrete. Cem Concr Res
29:497–501
35. Bai J, Wild S, Sabir BB (2002) Sorptivity and strength of
air-cured and water-cured PC-PFA-MK concrete and the
influence of binder composition on carbonation depth. Cem
Concr Res 32:1813–1821
36. Taşdemir C (2003) Combined effects of mineral admix-
tures and curing conditions on the sorptivity coefficient of
concrete. Cem Concr Res 33:1637–1642
37. Bakker RFM (1988) Chapter 3: initiation period, corrosion
of steel in concrete. In: Schiessl P (ed) RILEM Report of
the Technical Committee 60-CSC. Chapman and Hall,
London, pp 22–55
38. Bonavetti V, Donza H, Rahhal V, Irassar E (2000) Influ-
ence of initial curing on the properties of concrete con-
taining limestone blended cement. Cem Concr Res 30:703–
708