Construction and Building Materials 44 (2013) 175–184

Contents lists available at SciVerse ScienceDirect

Construction and Building Materials

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

Mechanical and durability properties of self consolidating high

performance concrete incorporating natural zeolite, silica fume
and fly ash
Fereshteh Alsadat Sabet ⇑, Nicolas Ali Libre, Mohammad Shekarchi
Construction Materials Institute (CMI), School of Civil Engineering, University of Tehran, Tehran, Iran

h i g h l i g h t s

 NZ can be properly used as a cement replacement in SCHPC.

 NZ and SF increase SP demand while FA increase fluidity at constant SP content.
 SF is more effective than NZ and FA in enhancing compressive strength.
 NZ and SF significantly improve durability properties specifically against chloride attack.
 NZ is slightly less effective than SF in improving durability, however it is much cheaper.

a r t i c l e i n f o a b s t r a c t

Article history: Mineral admixtures are widely used as cement replacement materials in both high performance concrete
Received 17 May 2012 (HPC) and self consolidating concrete (SCC). While the effect of mineral admixtures on rheological
Received in revised form 27 January 2013 properties of SCC and mechanical behavior of HPC has been investigated by many researchers, further
Accepted 26 February 2013
research is needed to optimize the effective dosage of these admixtures in self consolidating high perfor-
Available online 9 April 2013
mance concrete (SCHPC). Moreover, the effects of some mineral admixtures such as natural zeolite on
properties of SCHPC has not been well established yet. This paper discusses the effect of natural zeolite,
Keywords:
silica fume and fly ash on the properties of fresh and hardened concrete. Slump flow, superplasticizer
Self consolidating concrete
High performance concrete
demand, compressive strength, electrical resistivity, water absorption and chloride permeability were
Natural zeolite measured for all mixes. The test results indicate that incorporation of mineral admixtures generally
Fly ash improve mechanical and durability characteristics of the mixes. However, silica fume is slightly more
Silica fume effective than natural zeolite or fly ash in improving durability properties of SCHPCs, while natural zeolite
Mineral admixtures is much more cost effective.
Durability Ó 2013 Elsevier Ltd. All rights reserved.
Electrical resistivity
Water absorption
Chloride permeability

1. Introduction constructing heavily reinforced sections, improving in situ con-

Self consolidating concrete (SSC) is characterized with its excel-
lent fluidity such that it can flow under its own weight and fill
formworks with complicated shapes and congested reinforcement
without need for internal or external compaction. While, providing
these characteristics, SCC keeps its stability without segregation or
bleeding [1]. Over the last few years, the use of SCC has dramati-
cally increased [2]. SCC has many advantages compared to
conventional concrete. Some of its advantages are shortened con-
crete construction time due to increasing productivity levels,
⇑ Corresponding author. Tel.: +98 21 88973631; fax: +98 21 88959740.
E-mail address: Fereshteh.sabet@gmail.com (F.A. Sabet).
crete quality, reducing noise and injuries related to vibration and
casting works which leads to a better work condition, and the
excellent concrete surface quality [3].
On the other hand, high performance concrete (HPC) is a con-
crete that is designed to provide high strength and excellent dura-
bility. In order to benefit from both characteristics of SCC and HPC,
a new type of concrete has developed which is known as self con-
solidating high performance concrete (SCHPC). SCHPC exhibits
great flow ability and stability while providing high strength and
excellent durability properties. The special criterion for perfor-
mance of SCHPC is presented in Table 1 [4].
In order to achieve fresh criteria for SCHPC that is simultaneous
high fluidity and adequate stability during transportation and

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2013.02.069
176 F.A. Sabet et al. / Construction and Building Materials 44 (2013) 175–184

Table 1 and pores with the size of 3  104–4  104 lm. Small pores
Performance criteria from properties of SCHPC. and channels lead to a large specific surface area of 35–45 m2/g
Test method Criterion (internal and external) [28] and thus ability of natural zeolite to
SCC property absorb and lose water up to 30% of its weight. Because of unbal-
Slump flow 550–850 mm [5] ance of electrovalence in Al–O tetrahedroids, cations tend to bond
V-funnel 2–12 s [6] into micropores of the structure. These cations can be exchanged,
L-box 0.8–1.0 [7] and thus natural zeolite has the ability to exchange cations without
U-box 650 mm [1]
J-ring (SF-JF) 6 50 mm [8]
major changes in its structure. Natural zeolite has proved to have
Penetration 68 mm [9] pozzolanic properties in spite of its crystalline structure [29]. Large
Sieve segregation 618% [10] quantities of reactive SiO2 and Al2O3 in natural zeolite which react
Segregation column 610% [11] with Ca(OH)2, to form further calcium silicate and calcium alumi-
HPC property nosilicate is responsible for pozzolanic activity of this mineral
Air content by pressure method 4–8% [12] admixture [30]. It is reported that, although natural zeolite reduces
Compression using cylinders P20 MPa [13] (Early-age)
slump of concrete, it can prevent bleeding and segregation. As for
P40 MPa [13] (28 and 91 days)
Ultrasonic pulse velocity by portable P4575 m/s [14] hardened concrete, natural zeolite increases compressive strength
ultrasonic due to its pozzolanic property. Moreover it enhances durability of
non-destructive digital indicating tester conventional concrete by reducing concrete permeability and
Porosity by fluid displacement method 7–15% [15] especially improve resistance to alkali-aggregate reaction [31].
Absorption by water saturation technique 3–6% [16]
According to Najimi et al. [32], natural zeolite can be properly used
True electrical resistivity by Wenner probe P5–10 kX cm [17]
Rapid chloride ion penetration 62000 Coulombs [13] as a supplementary cementitious material in normally consoli-
Normal chloride ion penetration at 6 months 60.07% [13] dated concrete, regarding the environmental protection and
Resistance to freezing and thawing P0.8 [18] sustainable development. Chan and Ji [33] reported that pozzolanic
(after 300 cycles)
reactivity of natural zeolite is between that of silica fume and fly
ash. However, natural zeolite is much cheaper than silica fume
and it is abundantly deposited in some parts of the world like Chi-
na, Cuba, Japan, United States and Iran. It also can be easily quar-
placing, it is usually essential to use costly chemical admixtures ried and processed to be used in concrete. Nevertheless, the
and high cement content. Therefore, one of the disadvantages of effect of natural zeolite on properties of SCHPC has not been inves-
SCHPC is its high production cost compared to conventional con- tigated yet.
crete. Incorporation of high cement content has also other disad- In order to better understand the long-term properties of SCHPC
vantages such as high hydration heat and high autogenous incorporating mineral admixtures, self consolidating mixes con-
shrinkage. Besides, from the environmental point of view, cement taining natural zeolite, fly ash and silica fume (with 10% and 20%
production is associated with consumption of natural resources by cement weight) were made. The performance of mixes were
and high amounts of carbon dioxide emissions which can cause investigated in terms of slump flow of fresh concrete, compressive
serious environmental impacts. strength and electrical resistivity up to 180 days, water absorption
Replacing part of cement by mineral admixtures is a practical at the age of 28 days and chloride diffusion after 90 days of expo-
solution to reduce the cost of SCHPC specifically if the mineral sure. The findings of this paper will be useful for developing the
admixtures are wastes or industrial by-products. It has been re- use of mineral admixtures in SCHPC.
ported that by replacing up to 50% of Portland cement with mineral
admixtures, economically competitive SCC can be produced [19].
2. Experimental program
Incorporation of mineral admixtures is also inevitable to achieve
high strength and proper durability properties of SCHPC. In addi- 2.1. Materials
tion, when mineral admixtures replace part of cement, heat of
hydration and consequently thermal cracking and also problems A type II cement with an specific gravity of 3.14 and a fineness of 290 m2/kg has
been used. The source of natural zeolite (clinoptilolite type) used in this project was
associating with autogenous shrinkage will be reduced. Moreover
the mines from north of Semnan, Iran. Quantitative X-ray diffraction phase analysis
some mineral admixtures eliminate the need for Viscosity Modify- of natural zeolite of the mine has shown 90–95% zeolite in the mineralogy compo-
ing Agents (VMAs) and improve properties of concrete in fresh and sition [34]. Natural zeolite has a specific gravity of 2.20, a fineness of 320 m2/kg and
hardened state [20,21]. Incorporation of mineral admixtures also an average particle size of 16.84 lm. As presented in Table 2, the total content of
SiO2, Al2O3, and Fe2O3 in the zeolite was found to be approximately 75% which is
can lead to sustainable construction by conserving energy and re-
more than the minimum requirement (70%) specified in ASTM C 618 for natural
sources and reducing environmental pollution impact associated pozzolans.
with cement production [22,23]. Mineral admixtures such as fly Silica fume was obtained from Azna ferro-silicon alloy manufacture with a spe-
ash, limestone powder, blast furnace slag and silica fume has been cific gravity of 2.0 and a specific surface area of 22,500 m2/kg. Fly ash used has a
successfully used in SCC [24,25]. However, mineral admixtures like specific gravity of 2.22 and a fineness of 410 m2/kg. The chemical compositions of
the used cementitious materials are shown in Table 2.
silica fume are expensive and use of them is not cost-effective spe-
The coarse aggregate has a maximum size of 12.5 mm, a specific gravity of 2.78,
cially in developing countries. A very common mineral admixture and water absorption of 0.84%. The fine aggregate was well-rounded natural sand
is fly ash which is only available in countries with coal combustion with fineness modulus of 2.68, specific gravity of 2.7 and water absorption of
plants. In other regions of the world fly ash should be imported and 2.8%. The superplasticizer (SP) was polycarboxylic acid-based with a specific gravity
of 1.07 and solid content of 36%.
consequently its price will be high. Hence it is necessary to find
less expensive locally available alternative mineral admixtures
such as natural zeolite that has a price up to 4 times less than silica 2.2. Mix proportions

fume [26].
Natural zeolite is a mineral admixture which is widely used in
some regions of the world [27]. It is a type of crystalline alumi-
no-silicate and it has a three dimensional structure which is com-
posed by Si–O tetrahedroids and Al–O tetrahedroids. Natural
zeolite’s crystals have a honeycomb like structure with channels
Several SCHPC mixes were performed incorporating different replacement lev-
els of natural zeolite, silica fume or fly ash (0–20% weight of cement), in order to
evaluate and compare the effect of mentioned mineral admixtures on properties
of SCHPC. The water to cementitious materials ratio (w/cm) and total cementitious
materials content were kept 0.33 and 500 kg/m3 respectively. These values were
chosen after making several mixes with different w/cm and cementitious materials
contents, to obtain a concrete with both high performance and self consolidating
 F.A. Sabet et al. / Construction and Building Materials 44 (2013) 175–184 177

Table 2
Chemical compositions of binders.

Material Chemical analysis (% by mass)

SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O Loss of ignition
Cement (type II) 20.68 13.18 4.32 64.14 2.38 2.06 0.42 0.56 0.77
Natural zeolite 63.32 11.7 0.32 3.6 1.2 0.088 – – 8.49
Silica fume 92.5 0.9 0.8 1 1.6 – 0.4 0.35 1.7
Fly ash 59.44 34.04 0.52 4 1.46 0.42 – – 0.73

lating the increase in mass resulting from immersion in water for 30 min up to 72 h
Table 3 as a percentage of the mass of the dry specimen. The specimens were then placed in
Mix proportions of concrete mixes. boiling water for 5 h and their water absorption was calculated.
Component Control Z10 Z20 S10 S20 F10 F20 Permeable voids are the portion of the voids in concrete that can absorb water
or be emptied by immersing the concrete in water or drying it. These are the voids
3
Coarse aggregate (kg/m ) 656 656 656 656 656 656 656 that communicate to exterior surface of the concrete specimen or are intercon-
Fine aggregate (kg/m3) 984 966 947 959 935 966 948 nected with the surface. According to ASTM C642, permeable voids are considered
Water (kg/m3) 160 160 160 160 160 160 160 as the voids that can absorb water, or be emptied when immersing concrete in
Cement (kg/m3) 500 450 400 450 400 450 400 water and boiling, or drying it. Volume of permeable voids is calculated using the
Natural zeolite (kg/m3) 0 50 100 0 0 0 0 following equation:
Silica fume (kg/m3) 0 0 0 50 100 0 0
Fly ash (kg/m3) 0 0 0 0 0 50 100 CA
Volume of permeable voidsð%Þ ¼  100 ð2Þ
Superplasticizer (% binder) 1.3 2.1 2.9 1.9 2.4 1.1 0.8 CD

where A, C, and D are mass of oven-dried sample in air, mass of surface-dry sample in
air after immersion and boiling, and apparent mass of sample in water after immer-
sion and boiling, respectively.

2.3.4. Chloride diffusion

Fig. 1. A scheme of electrical resistivity measuring system.
properties. The weight ratio of fine aggregate to coarse aggregate was maintained at
about 1.5:1 for all of the mixes. Superplasticizer was adjusted to attain a slump flow
of 600 ± 25 mm. Detail of mix proportions are shown in Table 3.
2.3. Specimen preparation and testing methods
Samples were prepared according to NT Build 443 [36]. 75  150 mm cylindri-
cal specimens were cast and moist cured for 28 days. Afterwards, the cylinders were
sawn to provide a 75 mm thick slice from the specimen. In order to simulate one-
dimensional diffusion, the slices were sealed with epoxy polyurethane coating on
all sides except the sawn surface. These specimens were then immersed in a sodium
chloride solution with a concentration of 165 g/l and a temperature of 23 °C. After
an exposure period of 90 days, the specimens were removed from the salt solution.
A hole with a diameter of 45 mm was drilled to produce pulverized material sam-
ples at incremental depths from the uncoated face. The resulting powder samples
from each layer were collected separately to analyze acid-soluble chloride content
according to ASTM C 1152. The resulting output of the test is a plot of chloride con-
centration versus depth from the exposed surface. The chloride diffusion coefficient
(De), and surface concentration (Cs) were calculated from the established chloride
concentration profile based on Fick’s second law of diffusion and Crank’s solution
(Eqs. (3) and (4)).

The dry materials were mixed first. Then, after solving the superplasticizer into @C @2C
¼ Da 2 ð3Þ
the water, they were added to the mixer. Immediately after mixing slump flow of @T @x
mixes were determined. Then the concrete mixes were cast into cylinders of dimen-
  
sions 75  150 mm. After casting, all the specimens were left covered in the casting x
room for 24 h. After demoulding, the specimens were cured in water at 25 ± 3 °C
Cðx; tÞ ¼ C s 1  erf pffiffiffiffiffiffiffiffiffiffiffi ð4Þ
2 De  t
until the test age. The hardened concretes were tested for compressive strength,
electrical resistivity, water absorption and chloride diffusion. where x is the depth from the surface (m), t is the exposure duration (s), C(x, t) is the
chloride concentration at depth x and time t, Cs is the chloride concentration at the
surface, De is the apparent diffusion coefficient (m2/s), and erf is the error function as
2.3.1. Compressive strength
defined in the following equation:
From every concrete mix, three cylindrical specimens with the size of
75  150 mm were tested for compressive strength at the age of 3, 28, 90, and 2
180 days, according to ASTM C 39. erf ðzÞ ¼ pffiffiffiffi Rz ð5Þ
p 0
expðu2 Þdu

2.3.2. Electrical resistivity

Electrical resistivity of the concrete mixes was conducted on three
3. Results and discussion
75  150 mm cylinders for each concrete mix at the 3, 28, 90 and 180 days after
casting of concretes. The test was performed according to AC Impedance Spectrom-
etry (ACIS) method [35] using a concrete resistance meter with frequency range of The results of slump flow test, compressive strength and electri-
1–50 kHz. Fig. 1 shows the apparatus used to measure resistance of concrete sam- cal resistivity of test specimens up to 180 days, water absorption
ples. Fresh cement paste was used in order to provide the proper electrical connec-
and voids in concrete at 28 days, and chloride penetration test
tion between copper plate and concrete specimen. The resistivity was then
calculated by the following equation: are discussed separately in the following sub-sections. Incorpora-
tion of mineral admixtures, have both physical and chemical
AR
q¼ ð1Þ interactions with cement paste, which affects properties of HPSCC.
l
The physical interactions may be named as increasing the specific
where q is the resistivity (kX cm), A the area of specimen (cm2), R the resistance surface area of the binder and the changes in grading of solid mate-
(kX) and l the length of specimen (cm).
rials of the concrete that in turn affects packing density of concrete
particles. Mentioned effects contribute to changes in fresh proper-
2.3.3. Water absorption and permeable voids
This test was performed based on ASTM C642 method on three 75  150 mm
ties of HPSCC, specifically rheology, which in turn may have some
cylindrical specimens. After 28 days of moist curing, the specimens were oven- effects on hardened properties of this concrete. Moreover, chemical
dried for 72 h then the water absorption of each specimen was measured by calcu- interaction of mineral admixtures with cement can be explained as
178 F.A. Sabet et al. / Construction and Building Materials 44 (2013) 175–184
Fig. 2. Superplasticizer dosage of concrete mixes to obtain target fluidity.
pozzolanic reactions that consume present calcium hydroxide (CH)
in hardened concrete paste to form more calcium silicate hydrate
(CSH) gel. More CSH can improve microstructure of hardened con-
crete and thus improve mechanical and durability properties of the
latter.
3.1. Fresh properties
All the concrete mixes were designed to have a slump flow
diameter of 600 ± 25 mm which was achieved by using varying
amounts of superplasticizer. The slump flow of all concrete mixes
were in the range of 580–625 mm which is in agreement with cri-
teria for SCHPC mentioned in Table 1.
The superplasticizer dosage required to obtain target slump
flow of all concrete mixes is shown in Fig. 2. The superplasticizer
dosages of the mixes containing natural zeolite were 2.1% and
2.9% by mass of binder which are substantially higher than that
of the control mix (1.3%). The higher the replacement of cement
by natural zeolite, the more the SP is required to achieve the target
slump flow. This is probably due to the large amount of pores in
the frame structure and high surface area of natural zeolite which
in turn increases the quantity of water adsorbed on the particle.
For a given slump flow the water demand increases with greater
surface area of binder [37] thus more superplasticizer is needed
to maintain water content. Another reason may be the increasing
paste volume with incorporation of natural zeolite, since the spe-
cific gravity of natural zeolite is lower than cement. The increased
paste volume reduces the interlocking friction between solid parti-
cles (aggregate) of concrete therefore increase the fluidity of it.
Similar researches on conventional concrete also confirmed that
incorporation of natural zeolite increased the demand for SP
[38,39].
The use of silica fume also increased the SP demand of the
mixes. This result is in agreement with other researches. According
to Park et al. [40], the high surface area of silica fume particles can
increase adsorption of SP, which reduces the amount available in
solution on the surface of cement particles and, thus, decreases
fluidity of the cementitious mixes.
In spite of natural zeolite and silica fume, incorporating fly ash
in the mixes reduced the amount of superplasticizer to reach target
slump flow. As shown in Fig. 2, the superplasticizer dosage of
mixes containing fly ash was 0.2% and 0.5% less than the control
mix. The reason may be attributed to the spherical geometry of
fly ash particles which easily roll over one another and also can dis-
perse agglomeration of cement particles. The spherical shapes
reduce the friction at the aggregate-paste interface which produce
a ‘‘ball-bearing effect’’ at the point of contact [41]. Therefore the
fluidity of concrete mixes containing fly ash is higher and less
superplasticizer is demanded to reach target fluidity. Nehdi et al.
[19] also reported that replacing 50% of cement by fly ash de-
creased SP dosage required to gain desired slump flow, from 1.9
to 1.5 l/m3. This result is confirmed by Libre et al. [21], that using
10–50% fly ash enhanced fluidity of self consolidating mortars.
3.2. Compressive strength
The average compressive strengths of the mixes at the age of 7,
28, 90 and 180 days are presented in Fig. 3. The gain in compres-
sive strength continued over the 180 days curing period. The
28-days compressive strength of all concrete mixes was in the
range of 57–80.5 MPa while the 180-days compressive strength
varied from 61 to 87 MPa. As can be seen both early-age and la-
ter-age compressive strength of all concrete mixes were in agree-
ment with the performance criteria of SCHPC, as mentioned in
Table 1. Regardless of the replacement levels, natural zeolite, silica
fume, and fly ash increased the later-age compressive strength
compared to the control except for the Z20 mix.
The highest 28 days compressive strength was achieved for F20
mix (80.5 MPa), which contained 20% fly ash. Conversely, the low-
est level of compressive strength at 28 days was obtained for Z20
mix (57 MPa), which was produced with a 20% replacement of ce-
ment by natural zeolite. Natural zeolite at 10% replacement level
improved the compressive strength from 62 for the control mix
to 64.5 MPa (at 28 days), however as shown in Fig. 3, 20% replace-
ment of cement by natural zeolite caused 8% reduction (at 28 days)
in compressive strength, which could be related to the higher void
content in this concrete in comparison with other mixes which is
discussed later in Section 3.4. Another reason for this phenomenon
could be due to the effect of zeolite on the hydration process and
the hydration products of Portland cement. However, the mecha-
nism of zeolite interaction with hydration products is still under
debate and requires more investigations to be fully elucidated.
Incorporation of silica fume at both replacement levels also
increased the compressive strength, at the age of 28 days, from
62 MPa for the control mix to 75.5 and 79.5 MPa for the mixes con-
taining 10% and 20% silica fume, respectively. It can be noticed that
the effect of silica fume on improving compressive strength was
more significant than the effect of natural zeolite, which could be
attributed to the higher pozzolanic activity if silica fume than that
of natural zeolite [42]. This is also reported by Chan and Ji [33] that
silica fume is more effective than natural zeolite on increasing
compressive strength of high performance concrete. Similar results
were also reported in a previous work [42] for the compressive
strength of conventional concrete incorporating natural zeolite or
silica fume.
Replacing cement with 10% and 20% fly ash also raised the
28-day compressive strength from 62 for control mix to 67 and
80.5 MPa, respectively. Enhancement of compressive strength of
the mixes containing fly ash could be due to filling of the voids
between cement grains by smaller particles of fly ash and also to
pozzolanic reactivity of it. There is not a certain agreement on
the effect of fly ash on compressive strength of SCC mixes in the lit-
erature. Nehdi et al. [19] investigated SCC mixes incorporating high
volume fly ash. They reported that replacing 50% of cement by fly
ash will cause 50% decrease in compressive strength in comparison
with the control mix. Guneyisi et al. [43] and Gesoglu et al. [24]
also reported that incorporating 20–60% fly ash in SCC, results in
reduction of concrete strength. In another work it is shown that
using 15% fly ash did not have a significant influence on compres-
sive strength while using 35% fly ash decreased the latter to some
extent [25]. On the other hand Chan and Ji [33] found that fly ash at
5–15% replacement level increased compressive strength. The
diversity of the results could be due to the fact that effect of using
 F.A. Sabet et al. / Construction and Building Materials 44 (2013) 175–184
Fig. 3. Compressive strength of concrete mixes at various ages.
fly ash on compressive strength depends on the amount of fly ash
used in each cubic meter of concrete and also on the test age. It can
be concluded that using fly ash in high volume (more that 30%)
replacement reduces compressive strength while in lower amounts
(less than 30%), effect of fly ash on compressive strength is not
certainly determined.
3.3. Electrical resistivity
Electrical resistivity is one of the most effective features of con-
crete durability since it is a significant factor affecting corrosion in
reinforced concrete. Electrical resistivity of 20 kX cm is the mini-
mum limit for corrosion propagation of steel rebar, above which
corrosion will be low in concrete reinforcement [44]. In concrete
incorporating mineral admixtures with pozzolanic reactivity, the
electrical resistance will increase with the concrete age.
Electrical resistivity of concrete mixes at different ages is shown
in Fig. 4. It is seen that the later-age resistivity values obtained from
all mixes are much higher which indicates excellent protection
against corrosion of reinforcements. Incorporation of all mineral
admixtures caused significant increase in electrical resistivity of
concrete mixes especially at later ages, since pozzolanic reactions
typically occur in a slower rate. It also can be realized that the more
the replacement level of cement by mineral admixtures, the higher
the electrical resistivity recorded from concrete specimens.
The improving effect of natural zeolite on electrical resistivity of
SCHPC is almost the same as that effect of fly ash in all testing ages.
179
For instance at the age of 90 days, electrical resistivity of the mixes
incorporating 10% and 20% natural zeolite or fly ash was about 30
and 50 kX cm respectively which is about 3.5 and 6 times of resis-
tivity of the control mix (8.4 kX cm). Increasing effect of natural
zeolite on electrical resistivity of conventional concrete is also re-
ported by Ahmadi and Shekarchi [42]. By creating a finer pore size
distribution [38] and decreased ionic concentration [45] natural
zeolite increased electrical resistivity.
Concrete mixes containing silica fume; however, have consider-
ably higher records of electrical resistivity than mixes including
natural zeolite or fly ash. This difference is even further at later ages.
Resistivity of S20 mix is about the resistivity of Z20 and F20 mixes
in 3 day specimens (2.6–4.5 kX cm), while at the age of 28 days,
resistivity of S20 mix is 110 kX cm which is about 4.5 times the
resistivity of Z20 or F20 mixes. This may be attributed to the higher
pozzolanic reactivity of silica fume which results a denser structure
of the paste, since the paste phase of the concrete can be considered
to be more conductive than the aggregate phase [46]. The results of
current work are in agreement with the research work done by
Gesoglu et al. [24], they reported that incorporation of 20–60% fly
ash or 5–15% silica fume increased electrical resistivity of SCC, how-
ever silica fume was more effective than fly ash.
3.4. Water absorption
Another major factor affecting concrete durability is the resis-
tance of concrete to the ingress of aggressive ions. The absorption
180 F.A. Sabet et al. / Construction and Building Materials 44 (2013) 175–184
characteristics of concrete indirectly represent the porosity, it also
gives an understanding of the permeable pore volume and connec-
tivity between these pores.
Fig. 5 presents the results of water absorption after 30 min
(initial absorption) as well as the absorption after 72 h (final
absorption) for all the concrete mixes. As presented in Fig. 5a,
incorporation of mineral admixtures did not have a significant ef-
fect on initial water absorption of concrete mixes. However as for
the final absorption, all the mineral admixtures used for replacing
cement caused pronounced reduction in latter property of concrete
(Fig. 5b). In Fig. 5a, recommendation given by CEB [47] for absorp-
tion after 30 min is also presented. Considering the limits recom-
mended by CEB, all the concrete mixes investigated showed a
low absorption which indicated ‘‘good’’ concrete durability.
According to [13] a high quality concrete has final absorption of
less than 5%, thus all of concrete mixes could be accounted as
high-quality from absorption point of view. The low value of water
absorption obtained is attributed to limited pore connectivity and
reduced porosity of the mixes.
Among all mineral admixtures investigated in this study, the
most effective one in reduction of final absorption was silica fume.
The absorption decreased more with an increase in percentage of
silica fume replacement. Replacing cement by silica fume at 10%
and 20%, reduced final absorption from 4.5% to 2.76% and 2.57%
respectively. It is also reported by Nili and Afroughsabet [48] that
the use of silica fume in fiber reinforced concrete reduced water
absorption.
Fig. 4. Electrical resistivity of concrete mixes at the age of (a) 3, (b) 28, (c) 90 and (d) 180 days.
Incorporation of natural zeolite and fly ash also decreased final
water absorption, however these mineral admixtures were not as
effective as silica fume. For example using 10% fly ash or natural
zeolite reduced final absorption up to 20%, while incorporating
10% silica fume caused 39% reduction in final absorption.
Volume of permeable voids for different mixes is shown in
Fig. 6. There is a fine correlation between permeable voids and final
water absorption (Fig. 7a). The water absorption increases corre-
spondingly as the permeable voids increase. In Fig. 7b, relation
between permeable voids and compressive strength at 28 days is
presented. It is shown that as the volume of permeable voids in-
creases, the compressive strength decreases. Fig. 7 denotes that
there exists a linear relation between two aforementioned param-
eters. As mentioned in Section 3.2, incorporation of natural zeolite
at 20% replacement level, caused some reduction in compressive
strength. It could be related to the higher void content
(voids = 12.2%) in this concrete in comparison with other mixes
(voids = 7–11%) (Fig. 6). Indeed the increased void content
decreases the load carrying capacity of concrete.
3.5. Chloride diffusion
There exist different ways through which chloride ions ingress
into concrete, which include capillary suction, diffusion, migration
or combinations of these transport mechanisms. Ion ingress is a
general term for any mechanism that can result in mass transport
of ions for example (1) diffusion under concentration gradient, (2)
 F.A. Sabet et al. / Construction and Building Materials 44 (2013) 175–184 181

Fig. 5. Water absorption of various mixes and limits recommended by CEB [47] (a) after 30 min and (b) after 72 h.

nism of chloride ingress into concrete. Therefore the chloride ions

measured in this experimental study could be entered into con-
crete by different complicated phenomenon. However, the purpose
of this study is to investigate the effect of mineral admixture on
durability performance of SCHPC. Therefore, diffusion was consid-
ered dominant and the effect of mineral additives on the diffusion
coefficients were investigated and compared herein.
As the chloride ions penetrate into the concrete they can be at-
tached to various hydration products of the binder. Therefore total
chloride ions entered into the concrete consist of free chloride ions
which are present in pore solution, and bound chloride ions. Only
free chloride ions can move through concrete pores and penetrate
further to rebar and start the corrosion process. In this study chlo-
ride is measured as acid-soluble chloride (total chloride) as de-
scribed in ASTM C1152.
The chloride content profiles after 90 days of exposure, based
Fig. 6. Permeable voids in different concrete mixes.
on NT Build 443 [36], obtained for different concrete mixes, are
shown in Fig. 8. It can be seen that incorporation of mineral admix-
tures generally caused reduction in chloride content in various
mass transport under capillary suction, or (3) mass transport under
depths. This could be attributed to the improvement of the
hydraulic gradient. The reduction of internal relative humidity or
microstructure, which is caused by the refinement of concrete
the so-called self-desiccation of HPC could also affect the mecha-
pores in presence of pozzolanic mineral admixtures [24,49].

Fig. 7. Relation between permeable voids and (a) Compressive strength and (b) water absorption of concrete mixes.
182 F.A. Sabet et al. / Construction and Building Materials 44 (2013) 175–184
Fig. 8. Chloride content profiles for different concretes.
Fig. 9. Chloride content at the depth of 10 mm for different concretes.
Fig. 9 shows chloride content at the depth of 10 mm for various
SCHPCs. Chloride content at the depth of 10 mm for mixes incorpo-
rating silica fume was minimum (0.07% weight of concrete) among
three mineral admixtures for both replacement levels, which indi-
cated that silica fume was the most effective mineral admixture in
controlling chloride penetration. For Z10 and Z20 mixes, chloride
content at the depth of 10 mm were 0.15 and 0.10, respectively.
Among tested mineral admixtures, fly ash had least effect on chlo-
ride penetrability. Chloride content at 10 mm were 0.22 and 0.12
for F10 and F20 mixes, respectively, which are more than those
of SCHPCs containing natural zeolite or silica fume.
Fig. 10. (a) Chloride diffusion coefficient and (b) surface chloride concentration of different concretes.
In order to discuss the results more quantitatively, two param-
eters were calculated, i.e. an effective diffusion coefficient (De) and
the surface chloride content (Cs). The diffusion coefficients were
determined by means of non-linear regression analysis in accor-
dance with the least squares fit method for the corresponding
exposure age (90 days). Aforementioned parameters are presented
in Fig. 10.
It can be seen that although the surface chloride concentrations
for any of concretes containing mineral admixtures were higher
than the control mixes, effective diffusion coefficient and penetra-
tion parameter were smaller. Higher values of surface chloride
content obtained for mineral concretes could be attributed to the
bonding effect of pozzolans which prohibits chloride ions to pene-
trate more into concrete therefore chloride ions will concentrate
on the surface. Another explanation is that these mineral additives
form additional calcium aluminate hydrates in their reaction,
which then combines with chlorides to form Friedel’s salts [13].
Valipour et al. [50] reported similar results for surface chloride of
normal concrete containing mineral admixtures.
Incorporation of natural zeolite was found to decrease the effec-
tive diffusion coefficient by more than two times compared to the
control mix. Increasing replacement level of natural zeolite caused
more reduction in effective diffusion coefficient. This is due to
reduction in the total pore content and improvement of transition
zone structure between zeolite blended cement paste and aggre-
gates of hardened concrete. Use of fly ash also caused reductions
in effective diffusion coefficient and penetration parameter which
can be attributed to pozzolanic effect of fly ash and also chloride
binding by the aluminate phases during the ponding time. How-
ever fly ash was found to be less effective than natural zeolite. In
comparison, according to Chan and Ji [33], for high performance
 F.A. Sabet et al. / Construction and Building Materials 44 (2013) 175–184
concrete, natural zeolite or fly ash had a similar effect on chloride
ions ingress.
Among three investigated mineral admixtures, silica fume was
the most effective one in reducing chloride penetration into con-
crete. It is well known that silica fume facilitates densification of
the material microstructure and reduces the pore sizes and con-
nectivity which results in substantial reduction in chloride diffu-
sion in corresponding concretes. Using 10% silica fume reduced
effective diffusion coefficient by more than three times and a fur-
ther increase in silica fume content did not improve chloride diffu-
sivity significantly. This result is in agreement with results of other
researchers for high performance and normal concrete [25,51,52].
4. Conclusions
Based on the findings of this study, the following conclusions
could be drawn:
 The superplasticizer demand of the SCHPCs containing 10% and
20% natural zeolite was respectively 0.8% and 1.6% (% binder)
higher than that of the control mix due to high surface area of
its structure. Incorporation of silica fume also increased the
superplasticizer demand for 0.6 and 1.1 (% binder) for the mixes
with 10% and 20% silica fume. Use of fly ash, on the other hand,
decreased the superplasticizer demand to some extent.
 Natural zeolite at 10% replacement level improved the compres-
sive strength from 62 MPa for the control mix to 64.5 MPa (at
28 days), however 20% replacement of cement by natural zeo-
lite caused 8% reduction (at 28 days) in compressive strength.
Silica fume was the most effective mineral admixture in
enhancing compressive strength, incorporation of silica fume
increased the compressive strength, at the age of 28 days, to
75.5 and 79.5 MPa for the mixes containing 10% and 20% silica
fume respectively. Replacing cement with 10% and 20% fly ash
also raised the 28-day compressive strength to 67 and
81 MPa, respectively.
 Incorporation of all mineral admixtures caused significant
increase in electrical resistivity of concrete mixes especially at
later ages. Incorporation of natural zeolite and fly ash in
concrete mixes caused enhancement in electrical resistivity in
almost the same level in all ages. Using 10% and 20% natural
zeolite or fly ash in concrete mixes increased the 90-day resis-
tivity from 8.4 kX cm for the control mix to 30 and 50 kX cm.
At this age resistivity of S10 and S20 mixes were 54 and
231 kX cm, respectively. This may be attributed to the higher
pozzolanic reactivity of silica fume.
 The most effective investigated mineral admixture in reduction
of final absorption was silica fume. Replacing cement by silica
fume at 10% and 20%, reduced final absorption from 4.5% to
2.76% and 2.57% respectively. Incorporation of natural zeolite
and fly ash also decreased final water absorption, however lat-
ter mineral admixtures were not as effective as silica fume.
Using 10% fly ash or natural zeolite reduced final absorption
up to 20%, while incorporating 10% silica fume caused 39%
reduction in final absorption.
 Incorporation of 10% and 20% natural zeolite was found to
decrease the effective diffusion coefficient for 4.3  1012 and
4.9  1012 m/s2 respectively. Fly ash was found to be less effec-
tive than natural zeolite in reducing chloride diffusion. Incorpo-
rating 10% and 20% fly ash decreased effective diffusion
coefficient from 7.9  1012 to 4.7  1012 and 3.2  1012 m/
s2, respectively. Using 10% silica fume reduced effective diffu-
sion coefficient for 5.6  1012 m/s2 and a further increase in
silica fume content did not improve chloride diffusivity
significantly.
183
 Incorporation of natural zeolite as a mineral admixture
enhanced durability properties of SCHPCs. Although it was not
as effective as silica fume, natural zeolite has the advantage of
being cost-effective and easily processed. Generally, natural
zeolite could properly be used as a mineral admixture in SCHPC
specially in some regions of the world like China, Cuba, Japan,
the United States and Iran.
Acknowledgements
Present work was done with the financial support provided by
Construction Materials Institute (CMI) at university of Tehran.
The authors also are grateful of efforts of Mr. Ali Poorzarabi and
Ms. Sara Javidmehr for their collaboration in experimental work.
References
[1] Libre NA, Khoshnazar R, Shekarchi M. Repeatability, responsiveness and
relative cost analysis of SCC workability test methods. Mater Struct 2012:1–14.
[2] Xie Y, Liu B, Yin J, Zhou S. Optimum mix parameters of high-strength self
compacting concrete with ultra-pulverized fly ash. Cement Concr Res
2002;32(3):477–80.
[3] Khayat KH, Hu C, Monty H. Stability of SCC, advantages and potential
applications. In: RILEM international conference on self-compacting
concrete. Rilem Publications SARL; 1999. p. 143–52.
[4] Safiuddin M, West JS, Soudki KA. Hardened properties of self-consolidating
high performance concrete including rice husk ash. Cement Concr Compos
2010;32:708–17.
[5] SCCEPG. The European guidelines for self-compacting concrete: specification,
production and use. West Midlands, UK: Self-Compacting Concrete European
Project Group (SCCEPG), The European Federation of Concrete Admixtures
Associations; 2005.
[6] EFNARC. Specifications and guidelines for self-consolidating concrete. Surrey,
UK: European Federation of Suppliers of Specialist Construction Chemicals
(EFNARC); 2002.
[7] Brameshuber W, Uebachs S. Practical experience with the application of self-
compacting concrete in Germany. In: Proceedings of the second international
symposium on self-compacting concrete. Tokyo, Japan: COMS Engineering
Corporation; 2001. p. 687–95.
[8] Bui VK, Montgomery D, Hinczak I, Turner K. Rapid testing method for
segregation resistance of self-compacting concrete. Cement Concr Res
2002;32(9):1489–96.
[9] Perez N, Romero H, Hermida G, Cuellar G. Self-compacting concrete, on the
search and finding of an optimized design. In: Proceedings of the first North
American conference on the design and use of self-consolidating concrete.
Illinois, USA: Hanley-Wood, LLC; 2002. p. 101–7.
[10] ACI 237R-07. Self-consolidating concrete. ACI manual of concrete practice Part
1. Michigan, USA: American Concrete Institute; 2007.
[11] Khayat KH. Optimization and performance of air-entrained, self-consolidating
concrete. ACI Mater J 2000;97(5):526–35.
[12] Kosmatka SH, Kerkhoff B, Panareśe WC, MacLeod NF, McGrath RJ. Design and
control of concrete mixtures. 7th ed. Ottawa, Ontario, Canada: Cement
Association of Canada; 2002.
[13] Shetty MS. Concrete technology: theory and practice. New Delhi, India: S.
Chand and Company Ltd.; 2001.
[14] Hearn N, Hooton RD, Mills RH. Pore structure and permeability. In:
Significance of tests and properties of concrete and concrete-making
materials (ASTM STP 169C). Philadelphia, USA: American Society for Testing
and Materials; 1994.
[15] Vanwalleghem H, Blontrock H, Taerwe L. Spalling tests on self-compacting
concrete. In: Proceedings of the third international symposium on self-
compacting concrete. Bagneux, France: RILEM Publications; 2003.
p. 855–62.
[16] Hearn N. On the corrosion of steel reinforcement in concrete. In: Proceedings
of the first structural specialty conference. Montréal, Quebec: Canadian
Society for Civil Engineering; 1996. p. 763–74.
[17] Russell HG. ACI defines high-performance concrete. Concr Int
1999;21(2):56–7.
[18] Hwang SD, Khayat KH, Bonneau O. Performance-based specifications of self-
consolidating concrete used in structural applications. ACI Mater J
2006;103(2):121–9.
[19] Nehdi M, Pardhan M, Koskowski S. Durability of self-consolidating concrete
incorporating high-volume replacement composite cements. Cement Concr
Res 2004;34(11):2103–12.
[20] Dinakar P, Babu KG, Santhanam M. Durability properties of high volume fly ash
self compacting concretes. Cement Concr Compos 2008;30(10):880–6.
[21] Libre NA, Khoshnazar R, Shekarchi M. Relationship between fluidity and
stability of self-consolidating mortar incorporating chemical and mineral
admixtures. Constr Build Mater 2010;24(7):1262–71.
184 F.A. Sabet et al. / Construction and Building Materials 44 (2013) 175–184
[22] Oner A, Akyuz S. An experimental study on optimum usage of GGBS for the
compressive strength of concrete. Cement Concr Compos 2007;29(6):
505–14.
[23] Yang EH, Yang YZ, Li VC. Use of high volumes of fly ash to improve ECC
mechanical properties and material greenness. ACI Mater J [41] Wei S, Handong Y, Binggen Z. Analysis of mechanism on water reducing effect
2007;104(6):620–8.
[24] Gesoglu M, Guneyisi E, Ozbay E. Properties of self-compacting concretes made
with binary, ternary, and quaternary cementitious blends of fly ash, blast
furnace slag, and silica fume. Constr Build Mater 2009;23:1847–54.
[25] Elahi A, Basheer PAM, Nanukuttan SV, Khan QUZ. Mechanical and durability
properties of high performance concretes containing supplementary
cementitious materials. Constr Build Mater 2010;24:292–9.
[26] Afrand Tooska Co., 1 Nader Alley, Tohid Square, Tehran. <http://
www.anzymite.com/about_e.html>
[27] Feng NQ, Peng GF. Application of natural zeolite to construction and building
materials in China. Constr Build Mater 2005;19:579–84.
[28] Mumpton FA, editor. Mineralogy and geology of natural zeolites. New
York: Reprint of mineralogical society of America’s reviews in mineralogy;
1993.
[29] Mindess S, Young JF, Darwin D. Concrete. USA: Prentice Hall; 2002.
[30] Colella C. Natural zeolites. Stud Surf Sci Catal 2005;157:13–40.
[31] Feng NQ, Jia HW. Prevention of AAR in cement concrete with natural zeolite.
Concr Cement Prod 1995;2 [in Chinese].
[32] Najimi M, Sobhani J, Ahmadi B, Shekarchi M. An experimental study on
durability properties of concrete containing zeolite as a highly reactive natural
pozzolan. Constr Build Mater 2012;35:1023–33.
[33] Chan SYN, Ji X. Comparative study on the initial surface absorption and
chloride diffusion of high performance zeolite, silica fume and PFA concretes.
Cement Concr Compos 1999;21:293–300.
[34] Eftekharnejad J. Evaluation of zeolite occurrence in Aftar mine. Tehran: Special
Publications of Ministry of Industries and Mines of Iran; 1996.
[35] Gu Ping, Xie Ping, Beaudoin JJ, Brousseau R. AC impedance spectroscopy (II):
microstructural characterization of hydrating cement–silica fume systems.
Cement Concr Res 1992;23(1):157–68.
[36] NT Build 443. Concrete, hardened: accelerated chloride penetration. Nordtest
method; 1995.
[37] Safiuddin M. Development of self-consolidating high performance concrete
incorporating rice husk ash. Ph.D. thesis. Waterloo, Ontario, Canada:
University of Waterloo; 2008.
[38] Feng N, Li G, Zang X. High-strength and flowing concrete with a zeolitic
mineral admixture. ASTM Cement Concr Aggr 1990;12(2):61–9.
[39] Feng N, Yang H, Zu L. The strength effect of mineral admixture on cement
concrete. Cement Concr Res 1988;18(3):464–72.
[40] Park CK, Noh MH, Park TH. Rheological properties of cementitious materials
containing mineral admixtures. Cement Concr Res 2005;35:842–9.
of fine ground slag, high-calcium fly ash, and low calcium fly ash. Cement
Concr Res 2003;33(8):1119–25.
[42] Ahmadi B, Shekarchi M. Use of natural zeolite as a supplementary
cementitious material. Cement Concr Compos 2010;32:134–41.
[43] Guneyisi E, Gesoglu M, Ozbay E. Permeation properties of self-consolidating
concretes with mineral admixtures. ACI Mater J 2011;108(2):150–8.
[44] ACI Committee 222. Protection of metals in concrete against corrosion. ACI
222R-01. Farmington Hills, Michigan: American Concrete Institute; 2001.
[45] Feng N, Hao T. Mechanism of natural zeolite powder in preventing alkali–silica
reaction in concrete. Adv Cement Res 1998;10(3):101–8.
[46] Farnam Y, Behrouzikhah A, Sabet FS, Jalili SM, Shekarchi M. The effect of
cement content on concrete durability with respect to environmental
compatibility. In: Fourth international conference on construction materials:
performance, innovations and structural implications. Nagoya, Japan:
ConMat’09; 2009. p. 289–94.
[47] CEB–FIP. Diagnosis and assessment of concrete structures – state of art report.
CEB Bulletin, Euro-International Concrete Committee (Comité Euro-
International du Béton); 1989. p. 83–85.
[48] Nili M, Afroughsabet V. The long-term compressive strength and durability
properties of silica fume fuber-reinforced concrete. Mater Sci Eng A
2012;531:108–11.
[49] Nilsson LO, Poulson E, Sandberg P, Sorensen HE, Klinghoffer OH. Chloride
penetration into concrete, State of the Art, Transport processes. Corrosion
initiation, test methods and prediction models. In: Fredriksen JM, editor.
Report no. 53. The Road Directorate, Denmark; 1996. p. 151.
[50] Valipour M, Pargar F, Shekarchi M, Khani D. Study of variation in surface
chloride of concrete containing different pozzolans in Persian Gulf Region. In:
12th International conference on durability of building materials and
components. Porto, Portugal; 2011.
[51] Dousti A, Shekarchi M, Alizadeh R, Taheri-Motlagh A. Binding of externally
supplied in microsilica concrete under field exposure conditions. Cement
Concr Compos 2011;33:1071–9.
[52] Shekarchi M, Rafiee A, Layssi H. Long-term chloride diffusion in silica fume
concrete in harsh marine climates. Cement Concr Compos 2009;31:
769–75.