Transport properties in metakaolin blended concrete

M. Shekarchi
a
, A. Bonakdar
b
, M. Bakhshi
b
, A. Mirdamadi
a
, B. Mobasher
b,
*
a
Department of Civil Engineering, School of Engineering, University of Tehran, Tehran, Iran
b
Department of Civil, Environmental and Sustainable Engineering, Arizona State University, Tempe, AZ, USA
a r t i c l e i n f o
Article history:
Received 9 April 2009
Received in revised form 25 February 2010
Accepted 1 April 2010
Available online 28 April 2010
Keywords:
Blended cements
Diffusion
Durability
Metakaolin
Permeability
Resistivity
Transport properties
a b s t r a c t
One of the approaches in improving the durability of concrete is to use blended cement materials such as
y ash, silica fume, slag and more recently, metakaolin. By changing the chemistry and microstructure of
concrete, pozzolans reduce the capillary porosity of the cementitious system and make them less perme-
able to exterior chemical sources as well as reducing the internal chemical incompatibilities such as
alkalisilica reaction. This paper presents the results of a study on the transport properties and durability
characteristics of concrete containing different levels of metakaolin. Water penetration, gas permeability,
water absorption, electrical resistivity, chloride ingress, and alkalisilica reaction potential were studied
and their inter-relationships discussed. Results show that substituting optimum levels of metakaolin
improves different aspects of the transport properties and durability performance. At 15% replacement
level, compressive strength increased by 20%, while the water penetration, gas permeability, water
absorption, electrical resistivity and ionic diffusion had improvements of up to 50%, 37%, 28%, 450%,
and 47%, respectively and the 28-day ASR expansion for this mix was reduced as much as 82%. The min-
imum replacement level required for mitigating ASR and the relationship between physical and chemical
effects of metakaolin were discussed.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
Recent societal shift toward sustainable consumption and
growth applied to civil infrastructure systems requires the con-
struction materials to be designed and used with utmost attention
to their durability and long term response. A majority of design
codes and specications use the compressive strength of concrete
as the main criterion for design of concrete structures. Mechanical
properties which are functions of porosity could to some extent
provide indications of the transport properties of concrete; how-
ever they are not valid criteria for overall durability performances.
Major transport properties of concrete are permeation, diffusion,
sorption, and absorption through which the aggressive media pen-
etrate into the bulk of concrete and may cause gradual degradation
[1]. Pozzolanic materials including silica fume, y ash, slag, and
metakaolin have been used in recent decades for developing high
performance concrete with improved workability, strength and
durability. Pozzolanic reactions change the microstructure of con-
crete and chemistry of the hydration products by consuming the
released calcium hydroxide (CH) and production of additional cal-
cium silicate hydrates (CSH), resulting in an increased strength
and reduced porosity and therefore improved durability [2].
Commercially available since the mid-1990s, metakaolin (Al
2-
Si
2
O
7
) has been used as a pozzolan for high performance concrete
applications. This material is a thermally activated alumino-silicate
which is mostly manufactured by calcination of kaolin clay at the
temperature range of 700850 C [3]. It typically contains 50
55% SiO
2
and 4045% Al
2
O
3
and is considered as a high reactivity
natural pozzolan [4]. This study addresses the role of metakaolin
in improving the transport and durability properties of concrete.
2. Background
2.1. High reactivity metakaolin
Metakaolin differs mainly from most other pozzolanic materials
due to its high reactivity with calcium hydroxide, and its ability to
accelerate cement hydration [5,6]. Due to the high levels of silica
and alumina in metakaolin, the C/S ratio of the produced CSH
gel is expected to be greater than of silica fume and y ash [7].
Dunster et al. [8] studied the pozzolanic reactivity of metakaolin
and estimated that in its pure form, metakaolin reacts with up to
1.6 times its mass of CH, producing C
5
AS
2
H
5
which is an average
composition representing a mixture of CSH, C
4
AH
13
, CAH
6
and
C
2
ASH
8
. Lagier and Kurtis [9] showed that Metakaolin has a cata-
lyzing effect on cement hydration, leading to acceleration in the
reaction rates and increase in cumulative heat evolved during early
hydration. Using thermo-gravimetric analysis, Wild and Khatib
0950-0618/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.conbuildmat.2010.04.035
* Corresponding author. Tel.: +1 480 965 0141; fax: +1 480 965 0557.
E-mail address: Barzin@asu.edu (B. Mobasher).
Construction and Building Materials 24 (2010) 22172223
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[10] showed the CH consumption in the mixture reduces as the le-
vel of metakaolin replacement increases. After a year of curing, CH
content was as much as 50% lower in paste with 15% metakaolin.
Higher CH consumption is an indication of higher proportion of
CSH gel in concrete, implying improved microstructure. They re-
ported that the average pore diameter of paste (w/b = 0.3) de-
creased by 66% (0.0122 lm) for 20% metakaolin after 28 days of
curing.
Metakaolin improves the workability and constructability, and
positively affects the time and energy in nishing and pumping
of concrete, provided that proper superplasticizers are used. Brooks
et al. [11] reported a 30% reduction of slump when using 15%
metakaolin in concrete followed by a 20% retardation of setting
times. Moulin et al. [12] and Badogiannis et al. [13] reported retar-
dation in a range of 095% in initial setting time as well as 1464%
for nal setting time using 20% of different types of metakaolin.
These discrepancies could be attributed to the neness of different
metakaolins and the amount and performance of different plasti-
cizers in each test.
The mechanical properties of concrete improve with addition of
metakaolin at various substitution levels. Hobbs [14] studied the
early strength development of concrete with metakaolin and
showed that 10% and 20% metakaolin could increase the 6-h tensile
strength of concrete up to 25% and 50%, respectively. Zhang and
Malhotra [15] reported an increase of 28-day compressive strength
up to 10%, and improvement of modulus of elasticity by 8% in 10%
metakaolin concrete. Wild, Khatib, and Jones [16] showed that
after 28 days of curing, the compressive strength of concrete with
various metakaolin levels (530%) increased up to 32%, with an
optimum level of 20% metakaolin. Bonakdar et al. [17] reported
compressive strength increase of up to 20% for splitting tensile
strength of 10%, with 15% metakaolin. More recently, Khatib [18]
showed 36% increase of compressive strength (90 MPa) and 7% in-
crease of dynamic modulus (47 GPa) at 28 days for 15% metakaolin
with lower w/b ratios.
The effects of metakaolin on the transport properties of con-
crete have been of more interest in recent years. Khatib and Clay
[19] measured the water absorption of concrete by capillary suc-
tion after 90 days of curing and reported that for 15% metakaolin,
the coefcient of water absorption reduced by 30%. Courard et al.
[20] showed a reduction by 20% for water absorption was also re-
ported for 15% metakaolin (9.7% mass). Bakhshi et al. [21] reported
values of gas permeability coefcients (K
g
) for metakaolin concrete
with different w/b ratios of 0.350.65 to be 0.46.4 10
16
m
2
.
More recently, Badogiannis and Tsivilis [22] reported a decrease
of gas permeability of 50% (1.4 10
16
m
2
) in concrete with 20%
metakaolin. Zhang and Malhotra [15] showed that 10% metakaolin
can improve the resistance to chloride ion penetration by 88% (390
coulombs). Boddy et al. [23] reported that the bulk coefcients of
diffusion for concrete can reduce up to 70% in 12% metakaolin con-
crete. Courard et al. [20] showed 5% lower diffusion rate in 15%
metakaolin (1.2 10
12
m
2
/s). Coleman [24] showed that at a
10% replacement level, metakaolin can reduce the diffusion rate
of chloride ions up to 68% (1.1 10
12
m
2
/s) for w/b = 0.4 and
80% (2.6 10
12
m
2
/s) for w/b = 0.6. Badogiannis and Tsivilis [22]
also reported a decrease of chloride permeability of 90% (240 cou-
lombs) in concrete with 20% metakaolin.
The potential for alkalisilica reaction in metakaolin blended
concrete was reported Aquino et al. [25] who conducted acceler-
ated ASR test on mortar bars and reported expansion reductions
as much as 50% lower in metakaolin concrete. Ramlochan et al.
[26] showed that substituting 1015% of cement with metakaolin
reduces the two years ASR expansion of concrete prisms to
0.04%. Others including Sibbick et al. [27] and Walters et al. [28]
also showed that ASR could be mitigated by 1015% replacement
of cement by metakaolin. Jones [29] reported that between 1962
and 1979, about 260,000 tones of metakaolin was used in con-
struction of four dams in Brazil where local aggregates were highly
alkali-active; results showed that ASR was successfully mitigated
where metakaolin was used in concrete.
2.2. Transport properties and durability of concrete
Once the chemical species have penetrated into the body of
concrete via one or more transport mechanisms, degradation could
gradually initiate by their chemical and/or physical interactions
with other components. Depending on the type of attack, the trans-
port mechanism could involve the permeation of water, absorption
of aqueous solutions by capillary suction, diffusion of gaseous com-
pounds, or ionic diffusion of dissolved species. Therefore, durability
concerns need to address the transport properties rst. In most
durability-related phenomena such as alkalisilica reaction (ASR),
sulfate attack, carbonation, leaching, frost resistance and corrosion,
there exist one or more transport mechanisms involved causing
the movement of water and/or chemical ions into or out of con-
crete, enhancing a set of chemical reactions or physical actions
with gradual deterioration of the material. Recent guidelines for
concrete design, classify concrete based on its durability, with
transport characteristics serving as the main criteria [1].
The inter-relationship among various transport properties,
durability indicators, and mechanical response is the subject of
many investigations. Linear or exponential regressions are used
to obtain empirical equations from experimental data. Some of
the major correlation parameters are coefcient of water perme-
ability K
w
expressed in terms of intrinsic permeability (m
2
),
hydraulic conductivity (m/s), or water penetration (m or mm), as
well as coefcients of gas permeability K
g
(m
2
), gas diffusivity D
g
(m
2
/s) and ionic diffusivity D
i
(m
2
/s). Lawrence [30] studied the
relationship between K
g
and D
g
as shown in Fig. 1 using data from
1 day to 28 days of curing. This relationship was also studied by
Graf and Gube [31]. Bamforth [32] presented data on the relation-
ship between K
g
and K
w
. Grube and Rechenberg [33] as well as
Zhang and Gjorv [34] showed the variations of D
i
with K
w
. Sugiy-
ama et al. [35] on the other hand studied the relationship between
D
i
and K
g
. Ahmad et al. [36] showed the correlation between water
penetration and D
i
as shown in Fig. 2 for control and silica fume
blended concretes. To summarize these relationships, Kropp and
Hilsdorf [1] suggested using a general equation as K = CD
b
in which
K is permeability coefcient, D is diffusion coefcient, C is a con-
stant depending on the pore structure of the cementitious system
0.1 1 10 100
D
g
[x 10
-8
], m
2
/s
0.01
0.1
1
10
100
K
g

[
x

1
0
-
1
6
]
,

m
2
1 Day Curing
28 Days Curing
Data from Lawrence (1986)
Fig. 1. Correlation between coefcients of gas diffusion and gas permeability.
2218 M. Shekarchi et al. / Construction and Building Materials 24 (2010) 22172223
and b correlates with the permeating or diffusing substance (gas,
water, ion) and varies between 1.0 and 1.8.
3. Experimental program
3.1. Materials
Concrete samples were prepared with 0%, 5%, 10% and 15% (by
weight) replacement of portlend cement by metakaolin, and re-
ferred throughout as C, MK5, MK10, and MK15, respectively. The
metakaolin used was a commercially available natural pozzolan
imported from India. It is noted that for comparison purposes,
the test program also included a mixture with 10% silica fume re-
ferred as SF10. Physical and chemical properties of the cement, sil-
ica fume, and metakaolin used are presented in Table 1 and
compared with metakaolin from other references including the
work of Wild and Khatib [10] Poon et al. [4] and Justice and Kurtis
[6]. The X-ray diffraction (XRD) pattern of the metakaolin used in
this study is shown in Fig. 3, showing high amounts of quartz
phase in this pozzolan. The mix proportions for concrete samples
are presented in Table 2 in which water to binder (w/b) ratio of
0.38 was used in conjunction with a poly-carboxilate based
superplasticizer to achieve desired workability. The results for con-
trol and metakaolin mixes are presented in the following sections
accompanied by graphical presentation; Test results are compared
with the silica fume mixture and discussed in a separate section.
3.2. Test procedures
The setting time was measured using ASTM C-403 [37] on
150 150 600 mm specimens of fresh concrete by using the
mean value of three different points on each prism. Compressive
strength values were measured in accordance to BS-1881 [38]
method on 150 150 150 mm cube specimens with three repli-
cates for each concrete mix on 1, 3, 7, 14 and 28 days of curing.
Several aspects of concrete transport properties and durability per-
formance were studied. All the durability tests were performed
after 28 days of water curing. Water penetration (W.P.) test was
carried out in accordance with ISO/DIS 7031 [39] with three repli-
cate cylinders (150 150 mm) for each mix were subjected to
three levels of water pressure of 1, 2, and 7 atm. After breaking
the cylinders into two halves via splitting tensile test, penetration
1 10 100
D
i
[x 10
-12
], m
2
/s
10
100
W
.
P
.
,

m
m
Control (Cement)
Silica Fume Blended
Data from Ahmad et al (2008)
Fig. 2. Correlation between coefcient of ionic diffusion and water penetration.
Table 1
Physical and chemical properties of cement and metakaolin.
Current study Metakaolin in references
Cement Silica fume Metakaolin Wild and Khatib (1997) Poon et al. (2001) Justice and Kurtis (2007)
SiO
2
(%) 25.66 88.10 51.85 52.10 53.20 52.50
Al
2
O
3
(%) 5.09 0.70 43.87 41.0 43.9 44.50
Fe
2
O
3
(%) 3.86 1.82 0.99 4.32 0.38 0.90
CaO (%) 60.12 1.32 0.20 0.07 0.02 N/A
MgO (%) 1.27 1.37 0.18 0.19 0.05 N/A
K
2
O (%) 0.63 2.35 0.12 0.63 0.10 N/A
Na
2
O (%) 0.36 0.66 0.01 0.26 0.17 N/A
SO
3
(%) 2.42 0.33 0.00 0.00 0.00 N/A
Specic gravity (kg/m
3
) 3120 N/A 2600 N/A 2620 N/A
Blaine neness (m
2
/kg) 320 N/A 2300 N/A N/A N/A
Moisture content (%) 0.38 N/A 0.70 N/A N/A N/A
Loss on ignition (%) 0.98 2.34 0.57 N/A 0.50 N/A
0 10 20 30 40 50 60
0
50
100
150
200
250
Q
Q
Q
Q
Q
M M
M
Q: Quartz
M: Mulite
Fig. 3. X-ray diffraction (XRD) pattern for metakaolin.
Table 2
Mixture proportions for concrete samples.
Mix proportion (kg/m
3
)
C MK5 MK10 MK15
Cement (type II) 400 380 360 340
Metakaolin 0 20 40 60
MK replacement (%) 0 5 10 15
Coarse aggregate (25 mm max) 737 737 737 737
Fine aggregate (3.8 neness modulus) 996 996 996 996
Filler (sand powder) 111 111 111 111
Water 152 152 152 152
W/CM 0.38 0.38 0.38 0.38
Super plasticizer (sulphonated naphthalene) 3.2 3.2 4.0 4.8
SP (%) 0.8 0.8 1.0 1.2
M. Shekarchi et al. / Construction and Building Materials 24 (2010) 22172223 2219
of water was determined for six locations along each sample. Gas
permeability (G.P.) test was conducted following RILEM-TC 116
[40] using nitrogen gas in which permeability coefcient K
g
(m
2
)
was determined for a steady-state laminar ow, taking into ac-
count the compressibility of the gas. In this method, three replicate
concrete disks of 50 mm in thickness were cut from top, middle,
and bottom of original 150 300 mm cylinders. Water absorption
(W.A.) test was performed according to ASTM C-642 [41] on three
replicates of 75 mm diameter cylinder cores drilled from original
100 200 200 mm prism specimens. Electrical resistivity (E.R.)
test using impedance spectroscopy was performed as a measure
of pore connectivity. The test was applied to a 75 mmdiameter cyl-
inder core drilled from a well-saturated 100 200 200 mm
specimen. Chloride ingress is due to ionic diffusion into concrete
and is especially important in marine environments with severe
humidity and temperature conditions such as the Persian Gulf with
temperature of up to 35 C and RH of up to 76% with chloride con-
tent of up to 21.4 g/L [42]. Chloride permeability proles were
determined for concrete disks of 15 mm in diameter and 100 mm
in thickness. Specimens were cured for 28 days, and then stored
in NaCl solution with 165 g/L concentration for 5 months
(6 months total age). Chloride concentration at each depth was
measured using samples collected from six replicate measure-
ments at each prole depth following the chemical method in NT
BUILD 443 [43]. As an important example of durability perfor-
mance of concrete, the potential for alkalisilica reaction (ASR)
was studied using different levels of metakaolin. For these reac-
tions to occur, alkaline solution must penetrate into concrete, fol-
lowed by its reaction with the silica from aggregates. This test
was conducted in accordance with ASTM C-1567 [44] on three rep-
licates of 25 25 285 mm mortar prisms made with local reac-
tive ne aggregates. The relationship between ASR expansion
values and transport properties will be discussed in the following
section.
4. Results and discussion
4.1. Test results
Fig. 4 presents the initial and nal setting times for these sam-
ples. The initial setting time decreased as much as 20% with MK15
mix whereas for the nal setting time, no signicant changes were
observed in different concrete samples. The development of com-
pressive strength values are shown in Fig. 5. After 28 days of cur-
ing, compressive strength of control and MK mixtures ranged
from 50.0 2.4 MPa to 59.8 3.5 MPa, representing as much as
20% increase for MK15. Due to low w/b ratio, major strength gain
was achieved in the rst 14 days of curing. The test results for
transport properties are shown in Fig. 6ad for W.P., G.P., W.A.,
and E.R., respectively as a function of metakaolin replacement le-
vel. For MK15, water penetration was reduced as much as 50%
(equal to 5.0 2.3 mm penetration) and gas permeability de-
creased up to 40%. The lowest permeability recorded was
0.75 10
16
m
2
which is indicative of a ne microstructure and
low connectivity of the porosity network. All concrete samples
showed low water absorptions (less than 2%), this value was de-
creased by 30% for MK15 with 1.32 0.10% absorption. Results
indicate that the resistivity of concrete cores increased up to 5.5
times for MK15 with 14.4 KXm resistivity. According to CEB-192
[45], values higher than 2 KXm are resistant to corrosion, while
resistivity of less than 0.5 KXm implies high corrosion potential.
Therefore, all concrete mixes including the control t into resistant
category with MK15 with highest resistance to corrosion. The re-
sults for chloride concentration proles (for C and MK10 mixes)
are presented in Fig. 7. The values of coefcient of diffusion (D)
for C and MK10 were calculated using Ficks 2nd Law of diffusion
as 3.2 0.05 10
12
m
2
/s and 1.7 0.05 10
12
m
2
/s, respec-
tively. This shows a 47% reduction of ionic diffusivity of concrete
obtained in the metakaolin blended mix.
Replacement Level, %
0
2
4
6
8
10
12
14
S
e
t
t
i
n
g

t
i
m
e
,

H
r
:
M
i
n
Initial Setting
Final Setting
0 5 10 15
7:30
6:21
9:24
5:48
10:00
9:55 9:49
6:34
Fig. 4. Initial and nal setting times.
0 10 20 30
Time, Days
0
15
30
45
60
C
o
m
p
r
e
s
s
i
v
e

S
t
r
e
n
g
t
h
,

M
P
a
Control
MK 5
MK10
MK15
Fig. 5. Compressive strength test result.
(a)
(b)
(c)
(d)
0 5 10 15
MK Replacement Level, %
4
6
8
10
12 W
.
P
.
,

m
m
0.6
0.8
1
1.2
1.4
G
.
P
.

x
1
0
-
1
6
,

m
2
1.2
1.5
1.8
2. 1
W
.
A
.
,
%
0
4
8
12
16
E
.

R
.
,

K

m
Fig. 6. Effect of metakaolin replacement level on different transport properties.
2220 M. Shekarchi et al. / Construction and Building Materials 24 (2010) 22172223
Test results for ASR are shown in Fig. 8 (expansion vs. time) and
Fig. 9 (expansion vs. metakaolin level). The results indicate that at
5% replacement level, no signicant changes were observed, how-
ever MK10 and MK15 mixtures showed much lower expansions as
much as 70% and 80% compared to C. The average value of expan-
sion for control was 0.207 0.011% after 14 days of exposure and
0.332 0.019% after 28 days which are both much larger than the
traditional 0.1% expansion limit. In the case of MK5, MK10 and
MK15, the expansion values after 28 days of exposure are
0.332 0.031%, 0.088 0.005%, and 0.058 0.006%, respectively.
These results can be used to discuss the minimum replacement le-
vel required to mitigate ASR expansion. In this case, at least 10% of
cement needs to be replaced by metakaolin to reduce the expan-
sion and corresponding possible damages.
The quantitative test results for are presented in Table 3 for con-
trol (C), metakaolin mixes (MK5, MK10, MK15) and silica fume mix
(SF10). It can be seen that the performance of SF10 in improving
the transport properties of concrete can be placed between MK10
and MK15 where the values of water penetration, gas permeability,
water absorption, electrical resistivity, and ionic coefcient of
diffusion were improved by 30%, 37%, 20%, 320%, and 53%,
respectively.
4.2. Correlation between replacement level and measured parameters
Linear and exponential regressions were used to correlate the
performance of different mixes with the level of metakaolin
replacement. The results are summarized in Table 4 showing a
good correlation (R
2
> 90%) which implies the benecial effects of
metakaolin replacement on the transport properties. To demon-
strate the simultaneous effect of metakaolin on different transport
parameters in Fig. 10, the relationship of gas permeability, water
0 10 20 30 40
Ingress Depth, mm
0
0.2
0.4
0.6
0.8
C
h
l
o
r
i
d
e

C
o
n
t
e
n
t
,

%
Control
MK10
Fig. 7. Chloride ions ingress prole test result.
0 10 20 30
Time, Days
0
0.1
0.2
0.3
0.4
L
i
n
e
a
r

E
x
p
a
n
s
i
o
n
,

%
C
MK5
MK10
MK15
Fig. 8. ASR test result.
(b)
0 5 10 15
MK Replacement Level, %
0
0.1
0.2
0.3
A
S
R

1
4
-
D

E
x
p
.
,
%
0
0.1
0.2
0.3
A
S
R

2
8
-
D

E
x
p
.
,

%
(a)
Fig. 9. Effect of metakaolin replacement level on ASR expansion.
Table 3
Quantities of measured parameters for C, MK and SF (average + standard deviation).
Reps. C MK5 MK10 MK15 SF10
Initial setting time (h:min) 3 7:30 6:34 6:21 5:48 7:21
Final setting time (h:min) 3 9:49 9:55 9:24 10:00 11:08
28-Day strength (MPa) 3 50.0 2.4 53.6 2.1 55.0 5.0 59.8 3.5 62.9 3.6
W.P. (mm) 6 10.1 1.9 8.1 2.6 7.2 2.3 5.0 2.3 7.1 3.2
G.P. ( 10
16
m
2
) 1 1.20 1.10 0.94 0.75 0.76
W.A. (%) 3 1.83 0.05 1.79 0.08 1.60 0.09 1.32 0.10 1.47 0.14
E.R. (KXm) 1 2.6 4.3 7.2 14.4 11.1
Ionic diffusion ( 10
12
m
2
/s) 6 3.2 0.05 N/A 1.7 0.05 N/A 1.5 0.03
28-Day ASR expansion (%) 3 0.332 0.019 0.332 0.031 0.088 0.005 0.058 0.006 0.074 0.007
Table 4
Regressions for transport properties (y) vs. metakaolin replacement level (x).
W.P.
(mm)
G.P. (m
2
) W.A.
(%)
E.R.
(KXm)
28-Day
ASR (%)
Linear:
y = ax + b
a 0.324 3.02e-18 0.034 0.024 0.0216
b 10.03 122.4e-18 1.89 0.06 0.365
R
2
0.977 0.982 0.910 0.922 0.843
Exponential:
y = ae
bx
a 10.28 0.00 1.92 10.38 0.42
b 0.045 0.031 0.022 0.1 0.1338
R
2
0.956 0.962 0.891 0.996 0.883
M. Shekarchi et al. / Construction and Building Materials 24 (2010) 22172223 2221
penetration and water absorption values are presented. The mini-
mum values for improving durability are obtained around the ori-
gin with MK 15, while maximum values indicating a reduced
durability are obtained for the control mix.
4.3. Correlation among transport parameters
The inter-relationship of different transport properties is an
important tool in correlating mix formulations with long term
durability parameters. Water penetration, as an indicator of trans-
port properties, was chosen and the inter-relationship was deter-
mined with linear and exponential regressions. Table 5 shows
the equations with the correlation levels. It can be observed that
these transport parameters can properly be correlated with each
other, all implying ne microstructure.
4.4. Correlation between transport/durability parameters and
compressive strength
Since both mechanical and durability properties are inuenced
by the pore structure, the relationship between transport proper-
ties and compressive strength of concrete is of primary interest.
Table 6 shows the linear and exponential regressions in relating
different transport properties with 28 day compressive strength
results. The relationship between ASR expansion after 28 days of
exposure and compressive strength was also studied to examine
if strength can be a proper indicator of ASR durability. Fig. 11
shows this relationship with a much lower correlation value
(R
2
= 69%) which could be attributed to the performance of MK5
which has improved the strength and transport properties but
has not improved the durability of concrete in ASR exposure. The
relationships between physical and chemical effects of pozzolanic
materials in improving the durability of blended cements could
therefore play an important role in durability-based design of con-
crete materials and structures.
x10
-16
5
6
7
8
9
1.4
1.6
1.8
2
2.2
0.75
0.8
0.85
0.9
0.95
1
1.05
1.1
1.15 C
MK 5
MK 10
MK 15
W.A., %
W.P., mm
G.P., m
2
Fig. 10. 3-D presentation of gas permeability, water absorption and water penetration.
Table 5
Regressions between water penetration (y) and other transport properties (x).
G.P. (m
2
) W.A. (%) E.R. (KXm)
Linear: y = ax + b a 1.05e17 8.60 0.127
b 2.92 6.46 10.70
R
2
0.962 0.896 0.931
Exponential: y = ae
bx
a 1.70 0.99 11.02
b 1.47e16 1.22 0.018
R
2
0.970 0.951 0.973
Table 6
Regression formulations for transport properties (y) vs. compressive strength (x).
W.P.
(mm)
G.P.
(m
2
)
W.A.
(%)
E.R.
(KXm)
28-Day
ASR (%)
Linear:
y = ax + b
a 0.52 4.75e-
18
0.05 0.038 0.031
b 36.00 359.1e-
18
4.63 1.86 1.911
R
2
0.995 0.959 0.911 0.949 0.698
Exponential:
y = ae
bx
a 383 0.00 10.91 0.00 7942
b 0.072 0.049 0.035 0.16 0.199
R
2
0.996 0.956 0.907 0.972 0.770
45 50 55 60 65
28 Day Compressive Strength, MPa
0
0.1
0.2
0.3
0.4
0.5
A
S
R

2
8
-
D
a
y

E
x
p
a
n
s
i
o
n
,

%
Experiment
Linear Fit (Averages)
C
MK5
MK10
MK15
Y = -0.031 X + 1.911
R
2
= 0.698
Fig. 11. Correlation between 28-day ASR expansion and 28-day compressive
strength.
2222 M. Shekarchi et al. / Construction and Building Materials 24 (2010) 22172223
5. Conclusions
Experimental results of various transport properties of concrete
modied with metakaolin are presented. Use of metakaolin accel-
erated the initial set time of concrete; however the nal set time
remained unchanged. Compressive strength increased by the as
much as 20% with 15% metakaolin replacement while all speci-
mens showed strength in excess of 50 MPa after 28 days of curing.
Transport properties measured in terms of water penetration, gas
permeability, water absorption, electrical resistivity, and ionic dif-
fusion were improved up to 50%, 37%, 28%, 450%, and 47%, respec-
tively while ASR expansion was reduced as much as 82% in MK15
mix. The performance of 10% silica fume addition in improving the
transport properties was observed to t between the MK10 and
MK15 mixes. The compressive strength correlation with ASR dura-
bility performance was inferior to the correlations obtained with
the transport properties.
Acknowledgments
This paper was a part of an independent research project at the
Construction Materials Institute (CMI) at the University of Tehran.
The authors would like to appreciate Asan Ceram Co. for support-
ing the Project and providing metakaolin for this study.
References
[1] Kropp JK, Hilsdorf HK. Performance criteria for concrete durability. RILEM
Report 12. E&FN SPON, London, UK; 1995.
[2] Bentz DP, Garboczi EJ. Simulation studies of the effects of mineral admixtures
on the cement paste aggregate interfacial zone. ACI Mater J 1991;88(5):
51829.
[3] Sabir BB, Wild S, Khatib JM. On the workability and strength development of
metakaolin concrete. In: Dhir RK, Dyer TD, editors. Concrete for environmental
enhancement and protection. London, UK: E&FN Spon; 1996. p. 6516.
[4] Poon CS, Lam L, Kou SC, Wong YL, Wong R. Rate of pozzolanic reaction of
metakaolin in high-performance cement pastes. Cem Concr Res
2001;31:13016.
[5] Khatib JM, Wild S. Pore size distribution of metakaolin paste. Cem Concr Res
1996;26:154553.
[6] Justice JM, Kurtis KE. Inuence of metakaolin surface area on properties of
cement-based materials. ASCE J Mater Civil Eng 2007;19(9):76271.
[7] Zibara H, Hooton RD, Thomas MDA, Stanish K. Inuence of the C/S and C/A
ratios of hydration products on the chloride ion binding capacity of lime-SF
and lime-MK mixtures. Cem Concr Res 2008;38:4226.
[8] Dunster AM, Parsonage JR, Thomas MJK. The pozzolanic reaction of MK and its
effects on PC hydration. J Mater Sci 1993;28:1345.
[9] Lagier F, Kurtis KE. Inuence of Portland cement composition on early age
reactions with metakaolin. Cem Concr Res 2007;37:14117.
[10] Wild S, Khatib JM. Portlandite consumption in metakaolin cement pastes and
mortars. Cem Concr Res 1997;27:13746.
[11] Brooks JJ, Johari MAM, Mazloom M. Effect of admixtures on the setting times of
high-strength concrete. Cement Concr Compos 2000;2:2293301.
[12] Moulin E, Blanc P, Sorrentino D. Inuence of key cement chemical parameters
on the properties of metakaolin blended cements. Cem Concr Compos
2001;23:4639.
[13] Badogiannis E, Kakali G, Dimopoulou G, Chaniotakis E, Tsivilis S. Metakaolin as
a main cement constituent: exploitation of poor Greek kaolins. Cem Concr
Compos 2005;27:197203.
[14] Hobbs M. Effect of metakaolin in the fresh and hardened properties of
concrete. MEng project report, University of Surrey; 1966.
[15] Zhang MH, Malhotra VM. Characteristics of a thermally activated
aluminosilicate pozzolanic material and its use in concrete. Cem Concr Res
1995;25:171325.
[16] Wild S, Khatib JM, Jones A. Relative strength, pozzolanic activity and cement
hydration in superplasticised metakaolin concrete. Cem Concr Res
1996;26:153744.
[17] Bonakdar A, Bakhshi M, Ghalibaan M. Properties of high performance
concrete containing high reactivity metakaolin. In: Proceedings of the
seventh international symposium on the utilization of high-strength/high-
performance concrete. ACI-SP-228, ACI, Washington, DC; 2005. p. 28796.
[18] Khatib JM. Metakaolin concrete at a low water to binder ratio. Constr Build
Mater 2008;22:1691700.
[19] Khatib JM, Clay RM. Absorption characteristics of metakaolin concrete. Cem
Concr Res 2003;34:1929.
[20] Courard L, Darimont A, Schouterden M, Ferauche F, Willem X, Degeimbre R.
Durability of mortars modied with metakaolin. Cem Concr Res
2003;33:14739.
[21] Bakhshi M, Mahoutian M, Shekarchi M. The gas permeability of concrete and
its relationship with strength. In: Proceedings of the b, 2nd international
congress, June 58, 2006 Naples, Italy; 2006.
[22] Badogiannis E, Tsivilis S. Exploitation of poor Greek kaolins: durability of
metakaolin concrete. Cem Concr Compos 2009;31:12833.
[23] Boddy A, Hooton RD, Gruber KA. Long-term testing of the chloride penetration
resistance of concrete containing high-reactivity metakaolin. Cem Concr Res
2001;31:75965.
[24] Coleman NJ. Metakaolin as a cement extender. Ph.D. Thesis, University of
Aston; 1996.
[25] Aquino W, Lange DA, Olek J. The inuence of metakaolin and silica fume on the
chemistry of alkalisilica reaction products. Cem Concr Compos
2001;23:48593.
[26] Ramlochan T, Thomas M, Gruber KA. The effect of metakaolin on alkalisilica
reaction in concrete. Cem Concr Res 2000;30:33944.
[27] Sibbick RG, Nixon PJ. Investigation into the effects of MK as a cement
replacement material in ASR reactive concrete. In: Proceeding of 11th
international conference on AAR in concrete, Quebec; 2000. p. 76372.
[28] Walters GV, Jones TR. Effect of metakaolin on ASR in concrete manufactured
with reactive aggregates. In: Malhotra VM, editor. Proceeding of 2nd
international conference on durability of concrete, vol. 2, American Concrete
Institute; 1991. p. 9417.
[29] Jones TR. Metakaolin as a pozzolanic addition to concrete. In: Bensted J, Barnes
P, editors. Structure and performance of cements. Spon Press; 2001.
[30] Lawrence CD. Transport of oxygen though concrete. Brit Ceram Soc Proc
1986;35:2934.
[31] Graf H, Grube H. Einub der zusammensetzung und der nachbehandlung des
Beton auf seine gasdurchlassigkeit. Beton 1986;36(11):4269.
[32] Bamforth PB. The relationship between permeability coefcients for concrete
obtained using liquid and gas. Mag Concr Res 1987;39(138):311.
[33] Grube H, Rechenberg W. Betonabtrag durch chemisch angreifende saure
wasser. Beton 1987;37(11):44651.
[34] Zhang MH, Gjorv OE. Permeability of high-strength lightweight concrete. ACI
Mater J 1991;885:46370.
[35] Sugiyama T, Bremner TW, Tsuji Y. Determination of chloride diffusion
coefcient and gas permeability of concrete and their relationship. Cem
Concr Res 1996;26:78190.
[36] Ahmad S, Al-Kutti WA, Al-Moudi OSB, Maslehuddin M. Correlations between
depth of water penetration, chloride permeability, and coefcient of chloride
diffusion in plain, silica fume, and y ash cement concretes. ASTM
international. J Test Eval 2008;36(2):14.
[37] ASTM C-403. Standard test method for time of setting of concrete mixtures by
penetration resistance; 2008.
[38] BS 1881-116. Testing concrete. Method for determination of compressive
strength of concrete cubes; 1983.
[39] International Standards Organization (ISO). Concrete hardened. Determination
of the depth of penetration of water under pressure, Standard ISO/DIS 7031;
1983.
[40] TC 116-PCD. Tests for gas permeability of concrete preconditioning of
concrete test specimens for the measurement of gas permeability and capillary
absorption of water measurement of the gas permeability of concrete by the
RILEM CEMBUREAU method determination of the capillary absorption of
water of hardened concrete; 1999.
[41] ASTM C-642. Standard test method for density, absorption, and voids in
hardened concrete; 2006.
[42] Alizadeh R, Ghods P, Chini M, Hoseini M, Ghalibaan M, Shekarchi M. Effect of
curing conditions on the severe life design of RC structures in the Persian Gulf
region. J Mater Civil Eng, ASCE 2008;20(1):210.
[43] NT BUILD 443. Concrete, hardened: accelerated chloride penetration; 1991.
[44] ASTM C-1567. Standard test method for determining the potential alkalisilica
reactivity of combinations of cementitious materials and aggregate
(accelerated Mortar-Bar method); 2007.
[45] CEB-192. Diagnosis and assessment of concrete structures: state-of-the-art
report. Bulletin dinformation, Case Postale 88, CH-1015, Lausanne; 1989.
M. Shekarchi et al. / Construction and Building Materials 24 (2010) 22172223 2223