JOURNAL OF

COMPOSITE
Article M AT E R I A L S
Journal of Composite Materials
45(9) 1059–1064
! The Author(s) 2010
The effects of limewater on split tensile Reprints and permissions:
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strength and workability of Al2O3 DOI: 10.1177/0021998310378909
jcm.sagepub.com
nanoparticles binary blended concrete

Ali Nazari and Shadi Riahi

Abstract
The effect of limewater on split tensile strength and workability of Al2O3 nanoparticles binary blended concrete has been
investigated. Al2O3 nanoparticles with partial replacement of cement by 0.5, 1.0, 1.5, and 2.0 wt% have been used as
nanofillers. Curing of the specimens has been carried out in water and saturated limewater for 7, 28, and 90 days after
casting. The results indicate that Al2O3 nanoparticles up to maximum replacement level of 2.0% produces concrete with
improved split tensile strength but reduced workability when the specimens cured in saturated limewater with respect to
the specimens cured in water. Al2O3 nanoparticles can improve the filler effect and also the high pozzolanic action of fine
nanoparticles increases substantially the quantity of strengthening gel. Although the limewater reduces the strength of
concrete without nanoparticles, curing the specimens in saturated limewater results in more strengthening gel formation
in Al2O3 nanoparticles blended concrete causes high strength.

Keywords
Al2O3 nanoparticle, split tensile strength, workability, curing medium, concrete

Chimera Research Institute (2002). However, until

Introduction
Portland cement-based binders are the primary active
components of cementitious composites used in most
modern construction. The other components are water
and both fine and coarse aggregate. Binders are made
from Portland ‘clinker’ ground together with a little
calcium sulfate, and frequently also contain fine
mineral powders such as limestone, pozzolan (typically
volcanic ash), fly 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
cementitious composite for specific applications.
There are few reports on incorporation of nanopar-
ticles in cement-based composites. Li et al.1 investigated
the properties of cement mortars blended with nano-
particles to explore their super mechanical and smart
(temperature and strain sensing) potentials. Also, useful
applications of nano-SiO2 are addressed by the Fuji
now, research performed over the years has been
mainly aimed at achieving high mechanical perfor-
mance with cement replacement materials in micro
level. Several researchers have demonstrated that the
finer the SiO2 nanoparticle sizes in micron level, the
higher the compressive strength.2,3 But there is a
lack of knowledge on the effects of ultra fine and
nano-size nanoparticles on cementitious composite’s
properties.
Lu and Young4 achieved high strengths on com-
pressed samples, and Richard and Cheyrezy5 developed
reactive power concretes (RPCs). The development of
an ultrahigh strength cementitious composite was made
possible by the application of DSP (densified system
Department of Technical and Engineering Sciences, Islamic Azad
University (Saveh Branch), Saveh, Iran.
Corresponding author:
Ali Nazari, Department of Technical and Engineering Sciences, Islamic
Azad University (Saveh Branch), Saveh, Iran
Email: alinazari84@aut.ac.ir
1060 Journal of Composite Materials 45(9)

containing homogeneously arranged ultra-fine parti-
cles) with super plasticizer and silica fume content.6,5
Kuo et al.7 investigated the properties of waterworks
sludge ash cement paste incorporating SiO2 nanoparti-
cles. In their work, the flowability of the cement pastes
has been considered and shown that the flowability of
the cementitious composite decreases by increasing the
nanoparticle amount. Lin and Tsai8 investigated the
influences of nanomaterials on the microstructures of
sludge ash cement paste. They noticed that the amount
of crystallization in the hydrates increased with the
increased quantities of nanomaterial added.
Furthermore, denser crystallizations, smaller pore
sizes, and a decreased number of pores were observed
with the addition of nano-material results in decreasing
water permeability.
There are few works about incorporating other
nanoparticles in cementitious composites. For example,
Li et al.9,10 have investigated the compressive strength
and aberration resistance of cement paste composites
incorporating nano-Fe2O3 and nano-TiO2 nanoparti-
cles, respectively. Incorporation of zinc–iron oxide
nanoparticles as a replacement of cement have been
investigated by Flores-Velez and Dominguez.11
The other nanoparticles (such as ZrO2 and Cr2O3)
have rarely investigated and some of researchers do not
agree that the other nanoparticles could be pozzolans.
It seems that several works are needed to introduce
these new materials as cement replacement.
Previously, a series of works12–19 have been con-
ducted on cementitious composites containing different
nanoparticles evaluating the mechanical properties of
the composites.
In this study, the influence of nano-Al2O3 on split
tensile strength and workability of binary blended con-
crete cured in water and limewater have been
investigated.
Materials and methods
Ordinary Portland cement (OPC) conforming to
ASTM C15020 standard was used as received.
The chemical and physical properties of the
cement are given in Table 1. The nanoparticle size
distribution pattern of the used OPC has been illus-
trated in Figure 1.
Al2O3 nanoparticles with average nanoparticle size
of 15 nm and 40 m2/g Blaine fineness producing from
Suzhou Fuer Import & Export Trade Co., Ltd was used
as received. The properties of Al2O3 nanoparticles are
given in Table 2.
Locally available natural sand with nanoparticles
smaller than 0.5 mm, fineness modulus of 2.25, and
specific gravity of 2.58 g/cm3 (loose form) was used as
fine aggregate. Crushed basalt stored in the laboratory
with maximum size of 15 mm and specific gravity of
2.96 g/cm3 was used as coarse aggregate.

Table 1. Properties of Portland cement (wt%)

Chemical properties

Material SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O Loss on ignition
Cement 21.89 5.3 3.34 53.27 6.45 3.67 0.18 0.98 3.21
Specific gravity: 1.7 g/cm3 (loose form).

120

100
Percentage finer than

80

60

40

20

0
0 20 40 60 80 100 120 140 160
Particle size (μm)

Figure 1. Particles distribution pattern of ordinary Portland cement.

Nazari and Riahi 1061

Two series of mixtures were prepared in the labora-
tory trials. C0 series mixtures were prepared as control
specimens. The control mixtures were made of natural
aggregates, cement, and water. Series N were prepared
with different contents of Al2O3 nanoparticles with
average nanoparticle size of 15 nm. The mixtures were
prepared with the cement replacement of 0.5, 1.0, 1.5,
and 2.0 wt%. The water to binder ratio for all mixtures
was set at 0.40.21 The aggregates for the mixtures
consisted of a combination of crushed basalt and of
fine sand, with the sand percentage of 30 wt%.
The binder content of all mixtures was 450 kg/m3.
The proportions of the mixtures are presented
in Table 3.
Series N mixtures were prepared by mixing the
coarse aggregates, fine aggregates, and powder mate-
rials (cement and Al2O3 nanoparticles) in a laboratory
concrete drum mixer. The powder material in the series
C0 mixtures was only cement. They were mixed in dry
condition for 2 min, and for another 3 min after adding
the water. Slumps of the fresh concrete were determined
immediately to evaluate the workability following the
mixing procedure. Cylinders with the diameter of
150 mm and the height of 300 mm for split tensile
strength were cast and compacted in two layers on a
vibrating table, where each layer was vibrated for
10 s.22 The molds were covered with polyethylene
sheets and moistened for 24 h. Then, the specimens
were demolded and cured in water (N-W series) and
saturated limewater (N-LW series) at a temperature
of 20 C prior to test days. The split tensile strength
tests of the concrete samples were determined at 7,
28, and 90 days.
Split tensile test was carried out in accordance to the
ASTM C496 standard.23 After the specified curing
period was over, the concrete cylinders were subjected
to split tensile test by using universal testing machine.
Tests were carried out on triplicate specimens and aver-
age split tensile strength values were obtained.
Standard slump tests conforming to ASTM C14324
were used to determine the workability of the concrete.
Results and discussion
Split tensile strength
The split tensile strength results of series C0-W and
N-W mixtures are given in Table 4. Comparison of
the results from the 7, 28, and 90 days samples shows
that the split tensile strength increases with Al2O3
nanoparticles up to 1.0% replacement (N2-W) and
then it decreases, although the results of 2.0% replace-
ment (N4-W) is still higher than those of the plain
cement concrete (C0-W). It was shown that the use of
2.0% Al2O3 nanoparticles decreases the split tensile
strength to a value which is near to the control con-
crete. This may be due to the fact that the quantity of
Al2O3 nanoparticles (pozzolan) present in the mix is
higher than the amount required to combine with the
liberated lime during the process of hydration thus
leading to excess silica leaching out and causing a
deficiency in strength as it replaces part of the

Table 2. The properties of Al2O3 nanoparticles

Surface volume Density (g/cm3) Table 4. Split tensile strength of Al2O3 nanoparticle blended
Diameter (nm) ratio (m2/g) (loose form) Purity (%) cement mortars

15  5 163  20 <0.1 >99.9 Split tensile strength (MPa)

Sample Al2O3
designation nanoparticle (%) 7 days 28 days 90 days

C0-W (control) 0 1.5 1.8 2.3

Table 3. Mixture proportion of Al2O3 nanoparticles blended
concretes N1-W 0.5 2.2 2.3 2.6
N2-W 1.0 2.6 2.8 3.1
Sample Al2O3 Quantities (kg/m3) N3-W 1.5 2.4 2.5 2.8
designation nanoparticles
N4-W 2.0 1.8 1.9 2.3
Cement Al2O3 nanoparticles
C0-LW (control) 0 1.3 1.5 1.9
C0 (control) 0 450 0 N1-LW 0.5 2.4 2.9 2.9
N1 0.5 447.75 2.25 N2-LW 1.0 3.1 3.2 3.3
N2 1.0 445.50 4.50 N3-LW 1.5 3.5 3.4 3.4
N3 1.5 443.25 6.75 N4-LW 2.0 3.9 3.5 3.6
N4 2.0 441.00 9.00
Water to binder [cement + Al2O3 nanoparticles] ratio of 0.40.
Water to binder [cement + Al2O3 nanoparticles] ratio of 0.40, sand W denotes the specimens cured in water and LW denotes to those
492 kg/m3, and aggregate 1148 kg/m3. cured in saturated limewater.
1062
cementitious material but does not contribute to
strength.22 Also, it may be due to the defects generated
in dispersion of nanoparticles that causes weak zones.
The higher enhancement of split tensile strength in the
N series blended concrete are due to the rapid consum-
ing of Ca(OH)2 which was formed during hydration of
Portland cement specially at early ages related to the
high reactivity of nano-Al2O3 nanoparticles. As a
consequence, the hydration of cement is accelerated
and larger volumes of reaction products are formed.
Also, Al2O3 nanoparticles recover the nanoparticle
packing density of the blended cement, directing to a
reduced volume of larger pores in the cement paste.
Table 4 also presents the split tensile strength of
C0-LW and N-LW series. The results show that the
replacement of cement by Al2O3 nanoparticles up to
2.0 wt% (N4-LW) in N-LW series produces concrete
with high strength with respect to N-LW control con-
crete. By comparison the split tensile strength results of
C0-W and C0-LW series, it shows that after 7, 28, and
90 days of curing the concrete in the saturated limewa-
ter, the split tensile strength of the C0-LW series in
smaller than the corresponding strength of C0 series.
This may be due to more formation of crystalline
Ca(OH)2 in the presence of limewater which reduces
the split tensile strength in C0-LW series with respect
to C0-W series. On the other hand, the split tensile
strength of the N-LW series is more than those of
N-W series. Lime reacts with water and produces
Ca(OH)2 which needs to form C–A–H gel:25
CaO þ H2 O ¼ CaðOHÞ2 þHeat ð1Þ
When Al2O3 nanoparticles react with Ca(OH)2 pro-
duced from saturated limewater, the content of C–A–H
gel is increased because of high free energy of nanopar-
ticles which reduces significantly when reacts by
Ca(OH)2. The split tensile strength of N-W and
N-LW series should be compared from two viewpoints.
The first viewpoint is that the split tensile strength of
N-LW series increases by partial replacement of cement
with Al2O3 nanoparticles up to 2.0 wt% (N4-LW) while
for N-W series it increases by partial replacement
of cement with Al2O3 nanoparticles up to 1.0 wt%
(N2-LWand then decreases. Once more this confirm
the more C–A–H gel formation in the presence of
saturated limewater in which the quantity of Al2O3
nanoparticles (pozzolan) present in the mix is close to
the amount required to combine with the liberated lime
during the process of hydration thus leading to lesser
silica leaching out with respect to the specimens cured
in water. Second viewpoint is that the difference
between split tensile strengths of the N-W and N-LW
series after 28 days of curing is relatively high while this
difference in split tensile strength after 90 days of curing
Journal of Composite Materials 45(9)
is not high. This may be due to formation of crystalline
Ca(OH)2 in N-LW series after 28 days, which causes
reduction in split tensile strength. In the other words,
curing of the Al2O3 nanoparticles blended concrete in
saturated limewater after 28 days is completely suitable
to achieve high strength especially with high weight
percent of nanoparticles.
Workability
A high-quality concrete is one, which has acceptable
workability (around 6.5 cm slump height) in the fresh
condition and develops sufficient strength. Basically,
the bigger the measured height of slump, the better
the workability will be, indicating that the concrete
flows easily but at the same time is free from segrega-
tion.26,27 Maximum strength of concrete is related to
the workability and can only be obtained if the concrete
has adequate degree of workability because of self com-
pacting ability. Self-compacting repair mortars, as new
technology products, are especially preferred for the
rehabilitation and repair of reinforced concrete struc-
tures.28 The water/powder (cement, fly ash, limestone
filler, silica fume, nanoparticles, etc.) ratio of mortar
and the type of chemical admixtures should be deter-
mined, in order to place the fresh mortar without any
external compaction and at the same time without caus-
ing any segregation.29 In other words, the rheology of
paste phase of self-repairing mortar should have suit-
able properties from flowability and segregation point
of view.30–33
The workability of C0 and N series concrete are
presented in Figure 2. The figure shows the influence
of Al2O3 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
8
W
7 LW
6
Slump (cm)
5
4
3
2
1
0
C0 N1 N2 N3 N4
Figure 2. The effects of Al2O3 nanoparticles on workability of
concrete. N1, N2, N3, and N4 are the series N blended concrete
with 0.5%, 1.0%, 1.5%, and 2.0% of Al2O3 nanoparticles, respec-
tively. W denotes the specimens cured in water and LW denotes
to those cured in saturated limewater.
Nazari and Riahi
nano-Al2O3 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 reduc-
tion in workability in N-LW series is higher than that of
N-W series because of more rapid formation of C–S–H
gel results in a more viscose mortar with reduced
workability.
With the improvement of novel plasticizers, to
obtain high filling 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.34 The selection of
the amount and the type of cementitious or inert pow-
ders 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 poten-
tial), finest fraction content, Blaine fineness, and nano-
particle size distribution.
There is no universally accepted agreement on the
effect of these factors due to the complex influence of
the combination of these factors.35
Usually, increasing the fine nanoparticles content in
cements changes the rheological properties of pastes
and consequently influences the workability of mortars
and fresh concrete mixtures. The observed changes can
be advantageous or not as a result of many factors
influencing the rheology of cement pastes.36 It is usually
expected that, if the volume concentration of a solid is
held constant, for a specific workability, the replace-
ment of cement with a fine powder will increase the
water demand due to the increase in surface area.
This is more observed for nanoparticles blended con-
crete. However, in some cases, the above-mentioned
conclusion is not appropriate. Lange et al.37 obtained
same results with fly ash-blended concrete. But in this
study, the addition of nano-Al2O3 nanoparticles
decreased the fluidity and increased the water demand
for normal consistency.
Conclusions
The results show that the Al2O3 nanoparticles blended
concrete had higher split tensile strength compared to
that of the concrete without Al2O3 nanoparticles. It is
found that the cement could be advantageously
replaced with Al2O3 nanoparticles up to maximum
limit of 2.0% with average nanoparticle sizes of 15 nm
when the specimens cured at saturated limewater for
28 days. The optimal level of Al2O3 nanoparticles
content was achieved with 1.0% replacement for
the specimens cured in water 7, 28, and 90 days.
1063
Partial replacement of cement by Al2O3 nanoparticles
decreased workability of fresh concrete especially for
curing at saturated limewater.
References
1. Li H, Xiao HG, Yuan J and Ou J. Microstructure of
cement mortar with nano-particles. Compos Part B: Eng
2003; 35: 185–189.
2. Erdogdu K and Tucker P. Effects of fly ash nanoparticle
size on strength of Portland cement fly ash mortars. Cem
Concr Res 1998; 28: 1217–1222.
3. Lee SH, Sakai E, Diamond M and Bang WK.
Characterization of fly ash directly from electrostatic pre-
cipitator. Cem Concr Res 1999; 29: 1791–1797.
4. Lu P and Young JF. Hot pressed DSP cement paste.
Mater Res Soc Symp Proc 1992; 245: 321–328.
5. Richard P and Cheyrezy M. Reactive powder concretes
with high ductility and 200-800 MPa compressive strength.
San Francisco: ACI Spring Convention, SP, 1994,
pp.144–124.
6. Jo BW, Kim CH, Tae G and Park JB. Characteristics of
cement mortar with nano-SiO2 nanoparticles. Consrt
Build Mater 2007; 21(6): 1351–1355.
7. Kuo WT, Lin KL, Chang WC and Luo HL. Effects of
nano-materials on properties of waterworks sludge ash
cement paste. J Indian Eng Chem 2006; 12(5): 702–709.
8. Lin DF and Tsai MC. The effects of nanomaterials on
microstructures of sludge ash cement paste. J Air Waste
Manag Assoc 2006; 56: 1146–1154.
9. Li H, Xiao H and Ou J. A study on mechanical and
pressure-sensitive properties of cement mortar with nano-
phase materials. Cem Concr Res 2004; 34: 435–438.
10. Li H, Zhang M and Ou J. Abrasion resistance of concrete
containing nano-nanoparticles for pavement. Wear 2006;
260: 1262–1266.
11. Flores-Velez LM and Dominguez O. Characterization
and properties of Portland cement composites incorpo-
rating zinc-iron oxide nanoparticles. J Mater Sci 2002;
37: 983–988.
12. Nazari A, Riahi Sh, Riahi Sh, Shamekhi SF and
Khademno A. Mechanical properties of cement mortar
with Al2O3 nanoparticles. J Am Sci 2010; 6(4): 94–97.
13. Nazari A, Riahi Sh, Riahi Sh, Shamekhi SF and
Khademno A. The effects of incorporation Fe2O3 nano-
particles on tensile and flexural strength of concrete.
J Am Sci 2010; 6(4): 90–93.
14. Nazari A, Riahi Sh, Riahi Sh, Shamekhi SF and
Khademno A. Improvement the mechanical properties
of the concrete by using TiO2 nanoparticles. J Am Sci
2010; 6(4): 98–101.
15. Nazari A, Riahi Sh, Riahi Sh, Shamekhi SF and
Khademno A. Embedded TiO2 nanoparticles mechanical
properties monitoring in cementitious composites. J Am
Sci 2010; 6(4): 86–89.
16. Nazari A, Riahi Sh, Riahi Sh, Shamekhi SF and
Khademno A. Benefits of Fe2O3 nanoparticles in con-
crete mixing matrix. J Am Sci 2010; 6(4): 102–106.
17. Nazari A, Riahi Sh, Riahi Sh, Shamekhi SF and
Khademno A. Assessment of the effects of the cement
1064
paste composite in presence TiO2 nanoparticles. J Am Sci
2010; 6(4): 43–46.
18. Nazari A, Riahi Sh, Riahi Sh, Shamekhi SF and
Khademno A. An investigation on the strength and
workability of cement based concrete performance by
using TiO2 nanoparticles. J Am Sci 2010; 6(4): 29–33.
19. Nazari A, Riahi Sh, Riahi Sh, Shamekhi SF and
Khademno A. Influence of Al2O3 nanoparticles on the
compressive strength and workability of blended
concrete. J Am Sci 2010; 6(5): 6–9.
20. ASTM C150. Standard specification for Portland cement.
In: Annual book of ASTM standards. West
Conshohocken, PA: ASTM, 2001.
21. Zivica V. Effects of the very low water/cement ratio.
Constr Build Mater 2009; 23(8): 2846–2850.
22. AI-Khalaf MN and Yousift HA. Use of rice husk ash in
concrete. Int J Cem Compos Lightweight Concr 1984; 6(4):
241–248.
23. ASTM C496. Standard test method for splitting tensile
strength of cylindrical concrete specimens. West
Conshohocken, PA: ASTM, 2001.
24. ASTM C143. Standard test method for slump of hydraulic-
cement concrete. West Conshohocken, PA: ASTM, 2001.
25. Mostafa NY and Brown PW. Heat of hydration of high
reactive pozzolans in blended cements: isothermal con-
duction calorimetry. Thermochim Acta 2005; 435:
162–167.
26. Lin YH, Tyan YY, Chang TP and Chang CY. An assess-
ment of optimal mixture for concrete made with recycled
concrete aggregates. Cem Concr Res 2004; 34(8):
1373–1380.
27. Tattersall GH and Baker PH. An instigation of the effect
of vibration on the workability of fresh concrete using a
vertical pipe apparatus. Mag Concr Res 1989; 14(146):
3–9.
28. Courard L, Darimont A, Willem X, Geers C and
Degeimbre R. Repairing concretes with self-compacting
Journal of Composite Materials 45(9)
concrete: testing methodology assessment. In:
Proceedings of the First North American Conference on
the Design and Use of Self-consolidating Concrete,
Chicago, USA, 2002, pp. 267–274.
29. Felekoglu B, Tosun K, Baradan B, Altun A and Uyulgan
B. The effect of fly ash and limestone fillers on the
viscosity and compressive strength of self-compacting
repair mortars. Cem Concr Res 2008; 36: 1719–1726.
30. Banfill PFG. The Rheology of fresh cement and concrete:
a review. In: 11th International Cement Chemistry
Congress, Durban, 2003, pp. 13 .
31. Lemmer C, Hartman J and Wolf T. ‘Rheological Properties
of Mortars for Self-compacting Concrete,’ http://
www.massivbau.tu-darmstadt.de/user/ lemmer/web/scc/
LeDaCon199htm, 13 pp (accessed September 2003).
32. Ferraris CF and Gaidis JM. Connection between the rhe-
ology of concrete and rheology of cement paste. ACI
Mater J 1992; 88: 388–393.
33. Ferraris CF. Measurement of the rheological properties
of high performance concrete: state of the art report.
J Res Nat Inst Stand Technol 1999; 104: 461–478.
34. Cyr M, Legrand C and Mouret M. Study of the shear
thickening effect of superplasticizers on the rheological
behavior of cement paste containing or not mineral
admixtures. Cem Concr Res 2000; 30: 1477–1483.
35. Ferraris CF, Obla KH and Hill R. The influence of min-
eral admixtures on the rheology of cement paste and con-
crete. Cem Concr Res 2001; 31: 245–255.
36. Grzeszczyk S and Lipowski G. Effect of content and
nanoparticle size distribution of high-calcium fly ash on
the rheological properties of cement pastes. Cem Concr
Res 1997; 27: 907–916.
37. Lange F, Mortel N and Rudert V. Dense packing of
cement pastes and resulting consequences on mortar
properties. Cem Concr Res 1997; 27: 1481–1488.