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x
d
a
d
x
d
p
t
5
With
a
d
2
RTh
zFU
erf
1
1
2c
d
c
o
s
6
where D
cl
is the migration coefcient (m
2
/s), Z is valency, for chloride ions Z = 1, F is
Faraday constant, F = 9.649 10
4
J (V* mol)
1
, U is absolute potential difference (V),
R is gas constant, R = 8.315 J (K* mol)
1
, T is absolute mean temperature of the solu-
tions during the test (K), h is height of the test specimen (m), x
d
is mean penetration
depth of the chloride ions in each half of the test specimen (m), t is duration of the
test (s), erf
1
is inverse error function, c
d
is chloride concentration at which the col-
our changes, c
d
= 0.07 (mol/L ).
6. Results
6.1. Mechanical properties
6.1.1. Compressive strength
Table 3 shows the results of compressive strength of concrete
mixes at age of 28 and 91 days. It is clear that, the main factor,
which controls the compressive strength, is the w/b ratio. Mixes
8 and 9 with w/b ratio of 0.27 had the highest compressive
strength at both 28 days and 91 days. It was 82 MPa for mix 8 at
28 days and increased to 99 MPa after 91 days. In addition, the ce-
ment type has also an important role on the development of
strength especially at early ages. At 28 days, the compressive
strength of mix 1 with OPC was 62 MPa, however for mix 3 with
slag cement it was 52 MPa. Nevertheless, at 91 days both mixes
exhibited similar strengths (70 2 MPa). On the other hand, the
addition of pozzolanic materials has an important inuence on
concrete compressive strength; depending on its type, content
and properties. Combination of pozzolanic materials with Portland
cement enhances the strength of concrete more than with slag
cement as can observed from the results of mixes 2 and 7 respec-
tively. In addition, the strength improvement is more pronounced
Table 1
Physical and chemical properties of the used ne materials.
Material CaO SiO
2
Al
2
O
3
Fe
2
O
3
MgO Na
2
O K
2
O SO
3
Cl Specic density Surface area (cm
2
/g)
CEM I 63.25 20.8 4.61 2.59 4.17 0.16 0.50 2.70 3.17 3450
CEM III B 48 29.7 6.5 1.2 8 0.31 0.65 2.49 0.02 2.96 4156
Fly ash 3.1 49.2 27.6 7.6 2.1 0.9 5 5.0 2.29 2877
M20 5 52 25 6 1 1.5 1.9 1.1 2.45 6000
Silica fume 0.2 98.4 0.2 0.01 0.10 0.15 0.20 0.10 0.01 2.2 20,000
Quartz powder 98.5 0.7 0.06 2.69 2683
Quartz sand 0.013 99.6 0.11 0.012 0.004 0.006 0.024 2.67 760
Table 2
Composition of concrete mixes.
Mix Cement FA M20 SF SP Aggregate QS QP w/b Flow diameter Air content Fresh density
Type (%) (%) (%) (%) (kg/m
3
) (kg/m
3
) (kg/m
3
) (kg/m
3
) ratio (cm) (%) (t/m
3
)
1 CEM I 100 2.8 1854 46 84 0.42 52 1.5 2.45
2 CEM I 65 25 10 3 1854 46 84 0.42 46 1 2.46
3 CEM III 100 2.2 1854 46 84 0.42 53 1.5 2.43
4 CEM III 70 30 3.3 1854 46 84 0.42 52 1.3 2.45
5 CEM III 70 30 3 1854 46 84 0.42 51 1.3 2.44
6 CEM III 90 10 2.5 1854 46 84 0.42 48 2.3 2.42
7 CEM III 65 25 10 3 1854 46 84 0.42 50 2 2.44
8 CEM III 67 25 8 8.8 1947 48 88 0.27 44 1.5 2.50
9 CEM III 70 30 6.6 1947 48 88 0.27 48 1.4 2.49
228 M. Abd Elrahman, B. Hillemeier / Construction and Building Materials 58 (2014) 225233
in mixes with silica fume (mix 2 and 6). However, the strength
development of mix 4 with normal y ash is slow compared to
other mixes, particularly at early ages.
6.1.2. Modulus of elasticity
The experimental results of elastic modulus of concrete are
found in Table 3. All mixes have modulus of elasticity more than
40,000 MPa. Mix 8 with low w/b ratio has the highest elasticity
of about 51,000 MPa. Mix 1 and mix 3 showed roughly the same
elasticity, that mean slag cement and OPC have the same effect
on elasticity [20]. On the other hand, the elastic modulus of mixes
with silica fume is higher than mixes without silica fume. Mix 6
with silica fume showed the highest elasticity at w/b of 0.42, it
was 45,200 MPa. However, mix 4 with normal y ash showed the
lowest elastic modulus, it was 40,200 MPa.
6.2. Porosity measured with MIP
Table 4 presents the experimental results of concrete total
porosity at age of 91 days. Compared to literature, all mixes have
lower porosity than traditional concrete which lies between 15%
and 20% [21]. Mix 1 with OPC has the highest porosity (10%), while
the use of slag cement reduces the porosity to about 8.9% (mix 3).
However, replacing OPC by 25% ne y ash and 10% silica fume as
in mix 2 dramatically reduces the porosity to 6.2%. Moreover,
mixes 8 and 9 with low w/b ratio exhibited porosity in the range
of UHPC (about 46%) [21]. The total porosities of mix 8 and mix
9 were 3% and 4.9% respectively.
On the other hand, regarding durability and deterioration of
concrete, capillary porosity is of most concern. Most of the trans-
port mechanisms take place via the capillary pore framework.
Therefore, capillary porosity of concrete mixes has been calculated
from the data sheet of MIP measurements. It is assumed to be in
the range of 30 nm to 10 lm [21]. Table 4 shows also the capillary
porosity of different concrete mixes. Similar to total porosity re-
sults, mix 1 with w/b of 0.42 has the highest capillary porosity
(5.6%). At w/b ratio of 0.42, the capillary porosity of mix 2 was
4.5%. Mixes 8 and 9 with w/b ratio of 0.27 have very low capillary
porosity of 1.9% and 2.96% respectively. Fig. 4 presents the pore
size distribution of concrete mixes. Mix 1 has the largest volume
of pores in the size range of 0.010.1 lm. It is clear from the gure
also that combined addition of ne y ash and silica fume along
with the use of low w/b ratio (mix 8) resulted in large reduction
in pore sizes, particularly in the capillarity range.
6.3. Durability
6.3.1. Water penetration depth (permeability)
Table 5 illustrates the results of water penetration depth tests.
All mixes exhibited low permeability (depth < 20 mm). The results
revealed also that the main factor governs the permeability is the
w/b ratio. The penetration depth of mix 8 with w/b ratio of 0.27
was about 3 mm which is the lowest penetration depth, while
for mix 9 it was 5 mm. In addition, cementitious materials have
crucial inuences on pore volume and connectivity which control
the water permeation. Mix 5 with ne y ash has lower penetra-
tion than mix 4 with normal y ash; it was 8 and 18 mm respec-
tively. At the same time, mix 5 has lower depth than mixes 6
and 7 with silica fume. Mix 3 with slag cement showed higher
resistance to penetration than mix 1 with OPC (15 and 18 mm
respectively).
6.3.2. Absorption (capillary suction)
Table 5 shows the results of the absorption coefcient of differ-
ent concrete mixes. Mix 8 made with slag cement, ne y ash and
with w/b ratio of 0.27 has the lowest absorption coefcient of
about 0.08 kg/m
2
h
0.5
. However, for mix 1 with w/b ratio of 0.42
and with OPC, the water absorption coefcient was 0.32 kg/
m
2
h
0.5
, which is about 4 times higher than that of mix 8. All con-
crete mixes with slag cement have lower absorption than mix 1.
For all these mixes, the absorption coefcient ranges between 0.1
to 0.2 kg/m
2
h
0.5
. Compared to mix 1 with OPC, replacing a part
of OPC with 25% of ne y ash and 10% silica fume (mix 2) reduced
the absorption to about 0.1 kg/m
2
h
0.5
.
6.3.3. Chloride diffusion
Table 5 shows the experimental results of chloride diffusion
coefcient of concrete. Mixes with slag cement exhibited higher
resistance to chloride diffusion than mix 1 with OPC alone. How-
ever, mix 2 with partial replacement of OPC with silica fume and
ne y ash showed signicant reduction in the diffusion coef-
cient. It reduced from 28 10
13
m
2
/s for mix 1 to
4.5 10
13
m
2
/s for mix 2. At w/b ratio of 0.42, mix 5 with ne
y ash exhibited higher resistance to chloride diffusion than mix
6 with silica fume alone and higher than mix 7 with both silica
fume and ne y ash. Furthermore, due to incorporation of ne
y ash (mix 5), the chloride diffusion is reduced to around the half
of the value of mix 3 with slag cement only. As expected, reducing
the w/b ratio resulted in high resistance to chloride diffusion. With
w/b ratio of 0.27, combination of silica fume and ne y ash (mix
8) resulted in a very high reduction in chloride diffusion to
1.39 10
13
m
2
/s compared to mix 1 with w/b of 0.42 and OPC,
which is about 20 times less. On the other hand, contrary to the re-
sults of mixes with w/b ratio of 0.42, combination of silica fume
with ne y ash is more efcient in reducing the chloride diffusion
than ne y ash alone at w/b ratio of 0.27. Proof for that are the re-
sults of mixes 5, 7, 8 and 9. Similar conclusion has been empha-
sized by Bentz, who reported that silica fume is more efcient
for reducing diffusivity in low w/c ratio concretes [22].
Table 3
Compressive strength and modulus of elasticity of concrete mixes.
Mix Compressive strength (MPa) Modulus of elasticity (MPa)
28 days 91 days
Mix 1 62 72 43,100
Mix 2 78 82 44,500
Mix 3 52 68 43,500
Mix 4 56 64 40,200
Mix 5 68 72 42,900
Mix 6 66 78 45,200
Mix 7 66 71 40,800
Mix 8 82 99 50,200
Mix 9 80 91 46,900
Table 4
Total and capillary porosity of concrete mixes measured at the age of 91 days using MIP.
Mix Mix 1 Mix 2 Mix 3 Mix 4 Mix 5 Mix 6 Mix 7 Mix 8 Mix 9
Total porosity (%) 10.30 6.20 8.90 7.80 6.98 7.20 6.50 3 4.90
Capillary porosity
a
(%) 5.60 4.50 4.50 3.89 3.50 3.90 3.80 1.90 2.96
a
The capillary porosity is assumed to be in the range of 30 nm to 10 lm.
M. Abd Elrahman, B. Hillemeier / Construction and Building Materials 58 (2014) 225233 229
Fig. 4. Pore size distribution of concrete mixes measured at age of 91 days using MIP.
Table 5
Durability properties of concrete measured at age of 91 days.
Mix Water penetration depth (mm) Water absorption coefcient (kg/m
2
h
0.5
) Chloride diffusion coefcient 10
13
(m
2
/s)
Mix 1 18 0.32 28
Mix 2 14 0.095 4.5
Mix 3 15 0.178 9
Mix 4 18 0.132 8
Mix 5 8 0.105 3.81
Mix 6 11 0.148 6
Mix 7 13 0.15 5
Mix 8 3 0.074 1.39
Mix 9 5 0.088 4.33
230 M. Abd Elrahman, B. Hillemeier / Construction and Building Materials 58 (2014) 225233
7. Discussion
7.1. Mechanical properties
By having a close look to the experimental results, it can be ob-
served that the compressive strength and modulus of elasticity of
all mixes are higher than 60 MPa and 40 GPa respectively at
91 days with total cementitious materials of about 312 kg/m
3
.
However, for traditional concrete without optimization, the com-
pressive strength and modulus of elasticity are in the range of
about 40 MPa [21] and 25 GPA respectively. This signicant
enhancement in mechanical properties of concrete can be directly
attributed to the high packing density of solid particle system due
to applying ideal Fuller curve. On the other hand, the addition of
supplementary materials has important inuences on concrete
mechanical properties. The pozzolanic reaction turns CH into a
new pozzolanic CSH gel which tightens and strengthens the
aggregate-paste interface, therefore modulus of elasticity and late
strength are markedly improved. In addition, supplementary mate-
rials enhance the packing density which results in better compact-
ness, thus the strength increases [23]. These effects are more
noticeable with using ne y ash and silica fume.
In fact, it should be pointed out here that, at different w/b ratios
the behaviour of ne materials is somewhat different. At w/b ratio
of 0.42, the comparison of mix 5 and 7 showed that the compres-
sive strength and modulus of elasticity of mix 5 (72 and
42,900 MPa) with ne y ash was a little bit higher than mix 7
(71 and 40,800 MPa) with ne y ash and silica fume. While, at
low w/b ratio (0.27), the situation is totally reversed. The addition
of both silica fume and ne y ash (mix 8) enhanced the mechan-
ical properties (99 and 50,200 MPa) more than mix 9 with ne y
ash (91 and 46,900 MPa). On the other hand, although the cement
content is low (can be said lean mixes), the mechanical properties
of mixes 8 and 9 are in the range of high strength concrete which
needs more cement, more silica fume and more superplasticizer
per cubic meter. This can be reasoned by sequential lling of the
voids in the system. The voids between each particle class are lled
with particles from smaller class. Especially at the micro scale, the
gap between the cement particles and silica fume with average
diameter of about 30 lm and 0.5 lm respectively are lled with
ne y ash with diameter of 110 lm. As a consequence, the bond
between aggregate and cement paste is increased which improves
the mechanical properties as the experimental results revealed.
7.2. Porosity
In order to evaluate the experimental results, a small compari-
son with total and capillary porosity of concrete as reported in lit-
erature will be presented. It is stated that the total porosity of
normal concrete, HPC, and UHPC are 15%, 8.3% and 6% respectively,
while the capillary porosity (0.0310 lm) are 8.3%, 5.2% and 1.5%
by volume respectively [21]. The experimental results indicated
that the maximum total porosity was 10% for mix 1. In addition,
the capillary porosity was 5.6% which is lower than porosities of
conventional concrete as reported in the literature. These results
signicantly manifest the inuence of enhancing the packing den-
sity on concrete porosity. The porosity of concrete is resulted from
the porosity of cement paste only, however the voids inside the
aggregate do not participate in the porosity of concrete. By maxi-
mizing the packing density of aggregate, the volume of cement
paste (cementitious materials and water) required to ll the gaps
between the aggregate is reduced to about 23%. In this investiga-
tion, the cement content is about 312 kg/m
3
and the water content
is about 131 liters (w/c = 0.42). So, the total volume of cement and
water (cement paste) equals about 230 liters for one cubic meter of
concrete (23%). However, normal high performance concrete needs
at least 400 kg cement and about 168 liters of water (w/c = 0.42).
The total volume of cement paste (cement and water) is about
300 liters for one cubic meter of concrete (about 30%). So, if the ce-
ment pastes of both concrete have the same porosity, then the total
porosity of the densely packed concrete will be lower by 23.33%
because it has less cement paste.
The use of supplementary materials largely reduces the porosity
of concrete depending on their type and content at w/b ratio of
0.42. The use of slag cement, with higher neness than OPC, re-
duces the total and capillary porosity to about 9% and 4.5% respec-
tively (mix 3). More reduction of porosities was attained by the
addition of normal y ash (mix 4). The total and capillary porosities
were reduced to about 7.8% and 3.9% respectively. Mix 5 with ne
y ash showed lower porosity; about 7% and 3.5% for total and cap-
illary porosity respectively, which are smaller than the aforemen-
tioned porosities of HPC according to Teichmann [21]. This can
be attributed to the efcient packing of ne y ash which has small
size (<10 lm), spherical shape and smooth texture. On the other
hand, the addition of silica fume to the system of slag cement
and ne y ash showed a small effect at w/b ratio of 0.42. At the
same direction, mix 2 made with OPC, ne y ash and silica fume
exhibited about 6.3% and 4.5% for total and capillary porosity
respectively. At low w/b ratio, the porosity is signicantly reduced.
For mix 9 with w/b ratio of 0.27 and with ne y ash, the total and
capillary porosities were 4.9% and 2.9% respectively. More reduc-
tion was gained by the addition of the silica fume to the system.
The total and capillary porosity of mix 8 was about 1.9% 3% respec-
tively which are much lower than normal HPC [24]. These values
are comparable to those of UHPC which needs more nes, cement,
llers and superplasticizer and special mixing procedures.
7.3. Durability
The incorporation of ne y ash or both ne y ash and silica
fume with low w/b ratio result in an effective reduction in the
transport of contaminants into concrete. The results of sorption
and chloride diffusion conrm this inuence. The water absorption
coefcient of mix 9 was about 0.09 kg/m
2
h
0.5
. However, combina-
tion of ne y ash and silica fume leaded to more reduction in
water absorption coefcient to 0.07 kg/m
2
h
0.5
. Similar results
were obtained for the chloride diffusion which is considered the
most important factor that can be used to evaluate the concrete
durability. The chloride diffusion coefcient of mix 1 without
pozzolanic materials was about 28 10
13
m
2
/s. However, the
use of slag cement (mix 3) reduced the diffusion to around
9.3 10
13
m
2
/s. The use of ne y ash at the same w/b ratio of
0.42 (mix 5) reduced the diffusion to about 3.8 10
13
m
2
/s. How-
ever, mix 8 with w/b ratio of 0.27 showed the lowest chloride dif-
fusion (about 1.4 10
13
m
2
/s) which is in the range of UHPC [21].
The role of high packing density in reducing the chloride diffusion
coefcient can be elucidated by comparing the result of mix 5 with
literature [25]. In spite of both concretes made with ne y ash, the
chloride diffusion of mix 5 is 3.8 10
13
m
2
/s which is 5 times
lower than that of Brandburger which was 1.5 10
12
m
2
/s. Fur-
ther, by the use of silica fume it is reported that the diffusion coef-
cient reduced to 1.5 10
12
which is half the resistance of mix 7.
The transport of liquids and gases takes place through the con-
tinuous pore system inside concrete. So, enhancing the packing
density reduces the penetration of contaminates into concrete.
The increased volume of aggregate closes the transport passes
and makes it longer. The experimental results of water penetration
test clarify the important role of the increased packing density in
transport mechanisms. All concrete mixes exhibited water pene-
tration depth lower than 20 mm which can be classied as imper-
meable concrete under aggressive conditions (<30 mm) according
M. Abd Elrahman, B. Hillemeier / Construction and Building Materials 58 (2014) 225233 231
to Neville [26]. Because of its higher neness, the use of slag ce-
ment results in lower permeability compared to OPC concrete
[20]. This is attributed to the dense microstructure and the low
CH concentration in the transition zone in slag cement concrete.
The addition of both ne y ash and silica fume notably reduces
the permeability and diffusivity [27]. The main effect of ne mate-
rials is the enhancement of transition zone properties and making
it denser. This zone is known as the locus of micro-cracks which
inuences not only the mechanical properties but also the perme-
ability and durability. Due to its high pozzolanity, ne y ash and
silica fume increase the homogeneity of the microstructure by
replacing CH crystals with additional CSH gel. Therefore, the
probability of micro-cracking is reduced and the transition zone
becomes thinner. Moreover, the size and content of capillary pores,
as well as the CH crystals concentration are reduced with progress
of the pozzolanic reaction. Furthermore, the produced CSH gel
blocks the pores, reduces its size and interrupts its connectivity.
In addition, it reduces the wall effect around the aggregate sur-
faces, thus allowing better packing of cement particles at the inter-
face between cement paste and aggregate.
7.4. The role of dense packing and ne y ash
To explain the role of the packing density and ne y ash on
concrete properties, it is worth to repeat the fact that all of the
studied mixtures prepared roughly with the same volume fractions
of aggregate and cementitious materials. Applying ideal Fuller
curve in the concrete mix design minimized voids content. These
voids should be also lled with dense cement paste. However, ce-
ment particles with sizes of about 30 lm cannot achieve this tar-
get alone. Therefore, another material with smaller size which
can t in the voids between cement particles should be imple-
mented. Fine y ash is the ideal in these conditions because it
has smaller size, spherical shape, smooth texture and pozzolanic
reactivity. Going deeper, the voids between ne y ash should be
lled with smaller size particles. Silica fume with particle size of
about 0.10.5 lm could be the best material lling the voids be-
tween ne y ash. By this mechanism, cementitious materials
are needed only to ll the voids between the aggregates, which
are minimized, and also to cover the aggregate surface to keep
the workability at a satised level. As a result, dense microstruc-
ture are generated which enhances both mechanical properties
and durability of concrete using low binder content.
The role of ne y ash in reducing the porosity and enhancing
the concrete durability can be interpreted basically from several
aspects. Firstly, it enhances the packing density of the system by
its ball bearing effect which reduces the particle interlocking
[28]. Secondly, it enhances the packing of particles at the aggregate
surfaces. Thirdly, it reacts with CH, therefore, the transition zone
become denser and the pores become ner [29]. Fourthly, the poz-
zolanic reaction takes place within the capillary pores, and the
hydration products block and reduce the size of capillary pores
and prevent their connectivity. Fifthly, the pozzolanic reaction
takes some water of the free water in the system, which indirectly
reduces the porosity. Sixthly, it enhances the cohesion of fresh con-
crete and reduces the amount of bleeding water beneath the aggre-
gate, and as a result the transition zone is densied. Seventhly,
because of its spherical shape and smooth texture, it reduces the
water demand and makes the microstructure more homogenous.
Finally, because of its low hydration rate compared to cement,
the hydration heat is low which result in smaller thermal stresses
at early ages. Both normal y ash and ne y ash has similar inu-
ences on concrete from chemical point of view because they have
similar chemical composition as can be seen from Table 1. The only
difference is the mean particle size (neness): for normal y ash it
is in the range of cement (about 30 lm), while ne y ash it is
lower than 10 lm as can be seen in Fig. 3. The benets of ne y
ash instead of normal y ash can be drawn as follow:
1. Fine y ash is more reactive than normal y ash, therefore,
mechanical properties are better enhanced particularly at early
ages [2931].
2. Normal y ash has relatively large particle size; therefore, it
cannot ll the voids between cement particles which resulted
in poor packing density on the cement matrix.
3. Fine y ash enhances the packing density on the aggregate sur-
face which cannot be achieved by normal y ash.
On the other hand, the use of silica fume with cement (binary
system) result in low packing density because of the high inter-
particle forces and the possibility of agglomeration. Silica fume
should be uniformly and homogeneously dispersed in order to
achieve its pozzolanic and ller effects [32]. Therefore, the use of
adequate cementitious materials with optimum composition, with
the use of appropriate superplasticizer that is sufcient to ef-
ciently disperse the ne particles will lead to concrete with dense
microstructure and superior properties.
8. Conclusion
Based on the above results and discussions, the following con-
clusions can be drawn:
1. By applying ideal grading curve, it is possible to produce HPC
with superior properties using only 312 kg/m
3
of cementitious
materials.
2. In the densely packed system, replacing OPC with 25% ne y
ash and 10% silica fume (mix 2) exhibited compressive strength
higher than 80 MPa with w/b ratio of 0.42, while the elastic
modulus reached around 45 GPa. However, the compressive
strength reached 99 MPa and the elastic modulus was more
than 50 GPa for mix 8 with combination of slag cement, ne
y ash and silica fume along with w/b ratio of 0.27.
3. The maximum porosity of concrete mixes was 10% for mix with
OPC only, (signicantly lower than traditional concrete), which
revealed the importance role of packing density. However, a
total porosity of 3% has been achieved by using supplementary
materials with w/b ratio of 0.27.
4. A very low capillary porosity was obtained for all mixes com-
pared to traditional concrete and HPC. In particular, mix 8 with
w/b ratio of 0.27 has a capillary porosity of lower than 2%.
5. The optimized concrete showed very low water penetration
depth. At w/b ratio of 0.42, it ranges between 8 and 14 mm
and it decreased to 38 mm with reducing the w/b ratio to 0.27.
6. The chloride diffusion coefcient was reduced from
28 10
13
m
2
/s for OPC concrete to 4.5 10
13
m
2
/s by using
25% ne y ash and 10 silica fume. More reduction of chloride
diffusion is reached by using both silica fume and ne y ash
with slag cement at w/b ratio of 0.27, it is reduced to 1.39
10
13
m
2
/s (about 20 times lower than OPC concrete).
7. Silica fume is more effective in improving the durability and
strength of concrete in systems with loww/b ratio than systems
with high w/b ratio.
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