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Article history:
Received 21 December 2010
Received in revised form 15 January 2011
Accepted 27 February 2011
Keywords:
Al2 O3 nanoparticle
Compressive strength
Split tensile strength
Flexural strength
Percentage of water absorption
Curing medium
Concrete
TGA
XRD
Pore structure
a b s t r a c t
In the present study, the effect of limewater on strength and percentage of water absorption of Al2 O3
nanoparticles blended concrete has been investigated. Portland cement was partially replaced by Al2 O3
nanoparticles with the average particle size of 15 nm with different amount and the specimens were
cured in water and saturated limewater for specic ages. Utilizing up to 2.0 wt% Al2 O3 nanoparticles
could produce concrete with improved strength and water permeability when the specimens cured in
saturated limewater while this content is 1.0 wt% for the specimens cured in tap water. The high action of
ne nanoparticles substantially increases the quantity of CSH gel. Although the limewater reduces the
strength of concrete without nanoparticles when compared with that cured in water, curing the specimens in saturated limewater results in more strengthening gel formation around Al2 O3 nanoparticles
and causes improved permeability together with high strength. In addition, Al2 O3 nanoparticles are able
to act as nanollers and recover the pore structure of the specimens by decreasing harmful pores. Accelerated peak appearance in conduction calorimetry tests, more weight loss in thermogravimetric analysis
and more rapid appearance of peaks related to hydrated products in X-ray diffraction results, all indicate
that Al2 O3 nanoparticles could improve mechanical and physical properties of the specimens.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Portland cement-based binders are the primary active components of concrete used in most modern construction. The other
components are water and both ne and coarse aggregate. Binders
are made from Portland clinker ground together with a little calcium sulfate, and frequently also contain ne mineral powders
such as limestone, pozzolan (typically volcanic ash), y ash (usually from coal-burning power plants) and granulated blast furnace
slag. Such powders are referred to as supplementary cementitious
materials (SCMs) since they are used to replace some of the more
expensive clinker. Chemical admixtures such as superplasticizers
and air-entraining agents can be added in small amounts to modify the properties of a concrete for specic applications. Because
of ultrane size, nanoparticles show unique physical and chemical
properties different from those of the conventional materials. As a
result of their unique properties, nanoparticles have been gained
specic attention and been applied in many elds to fabricate new
materials with novelty functions. If nanoparticles are integrated
with traditional building materials, the new materials might possess outstanding or smart properties for the construction of super
high-rise, long-span or intelligent civil infrastructure systems [1].
Energy saving in building technology is one of the most important problems in the world. Reduction of energy usage can be
taken place even by design methods [2,3] or using waste materials [46]. Utilizing nanoparticles in the cement paste can produce
high strength concrete which is resistant to water permeability.
These two major parameters increase the performance and lifeservice of the specimen. There are several reports on incorporation
of nanoparticles in concrete specimens which most of them have
focused on using SiO2 nanoparticles [710] and TiO2 nanoparticles
[11,12]. There are a few studies on incorporating nano-Fe2 O3 [13],
nano-Al2 O3 [14], and nanoclay particles [15,16]. Additionally, a limited number of investigations are dealing with the manufacture of
nanosized cement particles and the development of nanobinders
[17]. Nanoparticles can act as heterogeneous nuclei for cement
pastes, further accelerating cement hydration because of their high
reactivity, as nano-reinforcement, and as nano-ller, densifying the
microstructure, thereby, leading to a reduced porosity. The most
signicant issue for all nanoparticles is that of effective dispersion.
The benecial action of the nanoparticles on the microstructure
and performance of cement-based materials can be explained by
the following factors [18,19]:
Table 1
Chemical and physical properties of Portland cement (wt%).
Material
SiO2
Al2 O3
Fe2 O3
CaO
MgO
SO3
Na2 O
K2 O
Loss on
ignition
Cement
21.89
5.3
3.34
53.27
6.45
3.67
0.18
0.98
3.21
1481
120
100
80
60
40
20
0
20
40
60
80
100
120
160
Table 2
The properties of nano-Al2 O3 .
Diameter (nm)
Density (g/cm3 )
Purity (%)
15 3
155 12
<0.12
>99.9
140
1482
Table 3
Mixture proportion of nano-Al2 O3 particles blended concretes.
Sample designation
Nano-Al2 O3 particles
C0 (control)
N1
N2
N3
N4
0
0.5
1.0
1.5
2.0
Quantities (kg/m3 )
Cement
Nano-Al2 O3 particles
450
447.75
445.50
443.25
441.00
0
2.25
4.50
6.75
9.00
Water to binder [cement + nano-Al2 O3 ] ratio of 0.40, sand 492 kg/m3 , and aggregate 1148 kg/m3 .
the center of prisms are used to measure pore structure. The samples are immersed in acetone to stop hydration as fast as possible.
Before mercury intrusion test, the samples are dried in an oven
at about 110 C until constant weight to remove moisture in the
pores. MIP is based on the assumption that the non-wetting liquid
mercury (the contact angle between mercury and solid is greater
than 90 ) will only intrude in the pores of porous material under
pressure [28,29]. Each pore size is quantitatively determined from
the relationship between the volume of intruded mercury and the
applied pressure [29]. The relationship between the pore diameter
and applied pressure is generally described by Washburn equation
as follows [28,29]:
D=
4 cos
P
(1)
where D is the pore diameter (nm), is the surface tension of mercury (dyne/cm), is the contact angle between mercury and solid
( ) and P is the applied pressure (MPa). The test apparatus used for
pore structure measurement is Auto Pore III mercury porosimeter.
Mercury density is 13.5335 g/ml. The surface tension of mercury
is taken as 485 dyne/cm, and the contact angle selected is 130 .
The maximum measuring pressure applied is 200 MPa (30,000 psi),
which means that the smallest pore diameter that can be measured reaches about 6 nm (on the assumption that all pores have
cylindrical shape).
Conduction calorimetry test was run out on a Wexham Developments JAF model isothermal calorimeter, using IBM program
AWCAL-4, at 22 C for a maximum of 70 h. Fifteen grams of cement
was mixed with water and saturated limewater and admixture
before introducing it into the calorimeter cell.
A Netzsch model STA 409 simultaneous thermal analyzer
equipped with a Data Acquisition System 414/1 programmer was
used for thermogravimetric analysis. Specimens which were cured
in water and saturated limewater for 90 days were heated from 110
to 650 C, at a heating rate of 4 C/min in an inert N2 atmosphere.
SEM investigations were conducted on a Hitachi apparatus.
Backscattered electron (BSE) and secondary electron (SE) imaging was used to study the samples, which were prepared under
conditions that ensured their subsequent viability for analytical
purposes.
A Philips PW-1730 unit was used for XRD analysis which was
taken from 4 to 70 .
3. Results and discussion
3.1. Compressive strength
The compressive strength results of C0-W and N-W series mixtures are shown in Fig. 4. By comparison the compressive strength
of the specimens cured for 7, 28 and 90 days, it could be observed
that the compressive strength increases with nano-Al2 O3 particles
up to 1.0% replacement (N2-W) and then it decreases, although the
results of 2.0% replacement (N4-W) is still higher than those of the
plain cement concrete (C0-W). It was shown that using 2.0% nano-
1483
Fig. 5. SEM micrograph of cement paste (a) without Al2 O3 nanoparticles and (b)
with Al2 O3 nanoparticles cured in water.
Fig. 6. XRD results of cement pastes at 15 h of curing for specimens (a) without Al2 O3 nanoparticles cured in water, (b) with Al2 O3 nanoparticles cured in water, (c) without
Al2 O3 nanoparticles cured in saturated limewater and (d) with Al2 O3 nanoparticles cured in saturated limewater.
1484
(1)
Fig. 7. SEM micrograph of cement paste (a) without Al2 O3 nanoparticles and (b)
with Al2 O3 nanoparticles cured in saturated limewater.
Fig. 7a and b shows the SEM micrograph of concrete without and with Al2 O3 nanoparticles at 7 days of curing in saturated
limewater. Once again, the micrograph of the mixture containing
nano-Al2 O3 revealed a compact formation of hydration products
and a reduced content of Ca(OH)2 crystals. Moreover, No signicant
differences are evident between the microstructure of concrete
without nano-Al2 O3 cured in water or saturated limewater. In addition XRD results of the cement pastes with Al2 O3 nanoparticles
at 15 h of curing in saturated limewater have been illustrated in
Fig. 6. The longer pick intensity shows that the amount of Ca(OH)2
crystals which needs to formation of CSH gel is more for the
specimens cured in limewater rather the specimens cured in water
when Al2 O3 nanoparticles are used.
3.2. Split tensile strength and exural strength
The split tensile strength and exural strength results of C0 and
N series mixtures are shown in Fig. 8a and b, respectively. The
results again shows the better tensile strength in Al2 O3 nanoparticles blended concrete with respect to the control concrete specially
in high volume fraction of nanoparticles in concrete cured at
saturated limewater. This again may be due to more CSH gel
formation in the presence of nanoparticles especially for the specimens cured at saturated limewater after 28 days of curing.
Fig. 8. (a) Split tensile strength and (b) exural strength of nano-Al2 O3 particle
blended concrete specimens.
1485
Slump (cm)
7
6
5
4
LW
2
1
0
Fig. 9. Percentage of water absorption of nano-Al2 O3 particle blended concrete
specimens.
C0
N1
N2
N3
N4
Fig. 10. Workability of concrete containing Al2 O3 nanoparticles. N1, N2, N3 and N4
are the series N blended concrete with 0.5%, 1.0%, 1.5% and 2.0% of Al2 O3 nanoparticles, respectively. W denotes the specimens cured in water and LW denotes to those
cured in saturated limewater.
concrete structures [35]. The water/powder (cement, y ash, limestone ller, silica fume, nanoparticles, etc.) ratio of mortar and the
type of chemical admixtures should be determined, in order to
place the fresh mortar without any external compaction and at the
same time without causing any segregation [36]. In other words,
the rheology of paste phase of self-repairing mortar should have
suitable properties from owability and segregation point of view
[3740].
The workability of C0 and N series concrete are presented in
Fig. 10. The gure shows the inuence of Al2 O3 nanoparticles content on the workability of mixtures at constant water to binder ratio
of 0.40. The results show that unlike the C0 series, all investigated
nano-Al2 O3 nanoparticles blended mixtures had low slump values
and non-acceptable workability. This may be due to the increasing in the surface area of powder after adding nanoparticles that
needs more water to wetting the cement nanoparticles. The reduction in workability in N-LW series is higher than that of N-W series
because of more rapid formation of CSH gel results in a more
viscose mortar with reduced workability.
With the improvement of novel plasticizers, to obtain high lling rates is possible even for compound molding systems. The fresh
characteristics of concrete, strength and durability of mortars can
be improved by the addition of inert or pozzolanic [41]. The selection of the amount and the type of cementitious or inert powders
depends on the physical and physico-chemical properties of these
powders which are affecting the performance of fresh paste such
as nanoparticle shape, surface texture, surface porosity and rate of
superplasticizer adsorption, surface energy (zeta potential), nest
fraction content, Blaine neness and nanoparticle size distribution.
There is no universally accepted agreement on the effect of these
factors due to the complex inuence of the combination of these
factors [42].
Usually, increasing the ne nanoparticles content in cements
changes the rheological properties of pastes and consequently
inuences the workability of mortars and fresh concrete mixtures.
The observed changes can be advantageous or not as a result of
many factors inuencing the rheology of cement pastes [43]. It is
usually expected that, if the volume concentration of a solid is held
constant, for a specic workability, the replacement of cement with
a ne powder will increase the water demand due to the increase
in surface area. This is more observed for nanoparticles blended
concrete. However, in some cases, the above-mentioned conclusion is not appropriate. Lange et al. [44] obtained same results with
y ash blended concrete. But In this study, the addition of nanoAl2 O3 nanoparticles decreased the uidity and increased the water
demand for normal consistency.
0.0169
0.0148
0.0141
0.0145
0.0164
0.0148
0.0143
0.0135
0.0127
0.0116
0.0147
0.0143
0.0134
0.0138
0.0149
0.0136
0.0130
0.0124
0.0114
0.0106
0.0065
0.0067
0.0066
0.0067
0.0067
0.0064
0.0066
0.0065
0.0065
0.0064
0
+17.7
+21.01
+19.46
+9.73
0
+19.18
+22.7
+25.05
+29.94
51.4
42.3
40.6
41.4
46.4
51.1
41.3
39.5
38.3
35.8
0
+13.55
+25.02
+21.38
+7.11
0
+16.96
+22.51
+27.49
+32.46
37.53
32.445
28.14
29.505
34.86
35.91
29.82
27.825
26.04
24.255
Water to binder [cement + nano-Al2 O3 ] ratio of 0.40.
W denotes the specimens cured in water and LW denotes to those cured in saturated limewater.
0
+4.25
+8.56
+6.88
+1.52
0
+14.08
+15.94
+17.39
+19.15
9.99
9.5655
9.135
9.303
9.8385
10.143
8.715
8.526
8.379
8.2005
0
+15.00
+27.38
+22.38
+7.38
0
+25.00
+37.38
+42.38
+50.00
42
35.7
30.5
32.6
38.9
42
31.5
26.3
24.2
21
0
+2.70
+5.61
+3.95
+0.83
0
+8.59
+12.47
+17.18
+24.54
0.0481
0.0468
0.0454
0.0462
0.0477
0.0489
0.0447
0.0428
0.0405
0.0369
Few-harm
pores
(2050 nm)
Pore size
distribution
(mL/g(%))
Reduced
extent (%)
Value
(nm)
Reduced
extent (%)
Reduced
extent (%)
Value (%)
Reduced
extent (%)
Value
(nm)
Value
(mL/g)
Prosity (%)
Most probable pore
diameter
Total specic pore
volume
Sample designation
Table 4
Properties of the pores in N-SCC specimens.
Value
(nm)
Harmful pores
(50200 nm)
C0-W (control)
N1-W
N2-W
N3-W
N4-W
C0-LW (control)
N1-LW
N2-LW
N3-LW
N4-LW
Multi-harm
pores
(>200 nm)
0.0099
0.0088
0.0080
0.0085
0.0093
0.0091
0.0080
0.0071
0.0079
0.0087
Reduced
extent (%)
1486
1487
Table 5
Calorimetric results and weight loss (%) of the pastes in the range of 110650 C at 90 days of curing of concrete specimens.
Sample designation
C0-W (control)
N1-W
N2-W
N3-W
N4-W
C0-LW (control)
N1-LW
N2-LW
N3-LW
N4-LW
299.8
292.4
268.1
275.6
303.1
312.5
274.4
254.2
240.3
219.1
First peak
Second peak
Time (h)
Rate (W/kg)
Time (h)
Rate (W/kg)
1.4
1.3
1.1
1.2
1.4
1.6
1.5
1.4
1.2
0.9
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.5
0.5
15.1
14.9
13.2
14.2
15.3
15.8
14.7
12.7
11.0
9.5
2.5
2.5
2.3
2.4
2.5
2.6
2.4
2.2
2.2
2.0
12.2
13.2
13.4
13.3
13.1
12.7
13
12.7
12.3
11.9
4. Conclusions
The results show that the specimens containing Al2 O3 nanoparticles have signicantly higher strength with comparison to that
of specimens without nano-Al2 O3 particles at every age of curing. It is found that the cement could be advantageously replaced
with nano-Al2 O3 particles up to maximum limit of 2.0% with average particle sizes of 15 nm when the specimens cured at saturated
limewater. The optimum level of nano-Al2 O3 particles content was
achieved 1.0% for the specimens cured in water. Partial replacement of cement by nano-Al2 O3 particles decreased percentage of
water absorption of concrete specimens. However, the workability
of concrete was reduced by adding Al2 O3 nanoparticles and hence
plasticizers were added to improve the workability of the specimens. Al2 O3 nanoparticles could accelerate the appearance of the
rst peak in conduction calorimetry test which is related to the
acceleration in formation of hydrated cement products. Thermogravimetric analysis shows that Al2 O3 nanoparticles could increase
the weight loss of the specimens when partially added to cement
paste. More rapid formation of hydrated products could in presence of Al2 O3 nanoparticles which was conrmed by XRD results
could be the reason of more weight loss. The pore structure of self
compacting concrete containing Al2 O3 nanoparticles is improved
and the content of all mesopores and macropores is increased.
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